Compounds for electronic devices

ABSTRACT

The present invention relates to compounds of the formula (I) and to the use thereof in organic electronic devices, and to organic electronic devices which comprise compounds of the formula (I), preferably as hole-transport materials and/or as matrix materials, in particular in combination with a further matrix material.

RELATED APPLICATIONS

This application is a divisional application of application Ser. No.13/574,004, filed Jul. 19, 2012 which is incorporated by reference inits entirety for all useful purposes. Application Ser. No. 13/574,004 isa national stage application (under 35 U.S.C. §371) ofPCT/EP2010/007740, filed Dec. 17, 2010, which claims benefit of GermanPatent Application No. 10 2010 005 697.9, filed Jan. 25, 2010.

The present invention relates to compounds of the formula (I) and to theuse thereof in electronic devices and to electronic devices whichcomprise these compounds.

Organic semiconductor materials, such as the compounds according to theinvention, are being developed for a number of different applications inelectronic devices.

The structure of organic electroluminescent devices (OLEDs) in which thecompounds according to the invention can be employed as functionalmaterials is described, for example, in U.S. Pat. No. 4,539,507, U.S.Pat. No. 5,151,629, EP 0676461 and WO 98/27136.

Regarding the performance data of the organic electroluminescentdevices, further improvements are still necessary, in particular withrespect to broad commercial use. Of particular importance in thisconnection are the lifetime, the efficiency and the operating voltage ofthe organic electroluminescent devices and the colour values achieved.In particular in the case of blue-emitting electroluminescent devices,there is potential for improvement with respect to the lifetime of thedevices.

In addition, it is desirable for the compounds for use as organicsemiconductor materials to have high thermal stability and a highglass-transition temperature and to be sublimable without decomposition.

Furthermore, the voltage in the case of hole-transport materials inaccordance with the prior art generally increases with the layerthickness of the hole-transport layer. In practice, a greater layerthickness of the hole-transport layer would frequently be desirable, butthis often has the consequence of a higher operating voltage and poorerperformance data. In this connection, there is a demand for novelhole-transport materials which have high charge-carrier mobility,enabling thicker hole-transport layers to be achieved with only a slightincrease in the operating voltage.

Arylamine derivatives are known from the prior art as hole-transport andhole-injection materials. Materials of this type based onindenofluorenes are disclosed, for example, in WO 06/100896 and WO06/122630. The indenofluorenamines described above have disadvantages inprocessability: during the vapour-deposition or coating process,premature deposition and thus complication of the industrial process mayoccur. In addition, the known hole-transporting materials frequentlyhave low electron stability, which results in short lifetimes of theelectronic devices comprising the compounds. There is a further need forimprovement here.

Furthermore, there is a demand for alternative matrix materials for usein electronic devices. In particular, there is a demand for matrixmaterials for phosphorescent emitters which simultaneously result ingood efficiency, a long lifetime and a low operating voltage. It isprecisely the properties of the matrix materials that are frequentlylimiting for the lifetime and efficiency of the organicelectroluminescent device.

In accordance with the prior art, carbazole derivatives, for examplebis(carbazolyl)biphenyl, are frequently used as matrix materials. Thereis still potential for improvement here, in particular with respect tothe lifetime and glass-transition temperature of the materials.Furthermore, there is a need for improvement with respect to theoperating voltage of the electronic devices comprising the materials inquestion.

Furthermore, ketones (WO 04/093207), phosphine oxides, sulfones (WO05/003253) and triazine compounds, such as triazinylspirobifluorene (cf.the application WO 05/053055 and the applications WO 10/015306 and WO10/072300), are used as matrix materials for phosphorescent emitters.Low operating voltages and long lifetimes are achieved, in particular,with ketones. There is still potential for improvement here, inparticular with respect to the efficiency and compatibility with metalcomplexes which comprise ketoketonate ligands, for exampleacetylacetonate.

Furthermore, metal complexes, for example BAlq orbis[2-(2-benzothiazole)phenolate]zinc(II), are used as matrix materialsfor phosphorescent emitters. There is still a need for improvement here,in particular with to the operating voltage and chemical stability.Purely organic compounds are frequently more stable than these metalcomplexes. Thus, some of these metal complexes are sensitive tohydrolysis, which makes handling of the complexes more difficult.

Also of particular interest is the provision of alternative materials asmatrix components of mixed-matrix systems. A mixed-matrix system in thesense of this application is taken to mean a system in which two or moredifferent matrix compounds mixed together with one or more dopantcompounds are used as the emitting layer. These systems are, inparticular, of interest in the case of phosphorescent organicelectroluminescent devices. For more detailed information, reference ismade to the unpublished application DE 102009014513.3.

Compounds known from the prior art which may be mentioned as matrixcomponents in mixed-matrix systems are, inter alia, CBP(biscarbazolylbiphenyl) and TCTA (triscarbazolyltriphenylamine) (cf.Example Part Table 4). However, there continues to be a demand foralternative compounds for use as matrix components in mixed-matrixsystems. In particular, there is a demand for compounds which effect animprovement in the operating voltage and lifetime of the electronicdevices.

For fluorescent OLEDs, the matrix materials used in accordance with theprior art, especially for blue-emitting electroluminescent devices, areespecially condensed aromatic compounds, in particular anthracenederivatives, for example 9,10-bis(2-naphthyl)anthracene (U.S. Pat. No.5,935,721). WO 03/095445 and CN 1362464 disclose9,10-bis(1-naphthyl)anthracene derivatives for use in OLEDs. Furtheranthracene derivatives are disclosed in WO 01/076323, WO 01/021729, WO04/013073, WO 04/018588, WO 03/087023 or WO 04/018587. Matrix materialsbased on aryl-substituted pyrenes and chrysenes are disclosed in WO04/016575. Matrix materials based on benzanthracene derivatives aredisclosed in WO 08/145239. For high-quality applications, it isdesirable to have available further matrix materials, which preferablyhave improved properties.

Prior art which may be mentioned in the case of blue-emitting compoundsis the use of arylvinylamines (for example WO 04/013073, WO 04/016575,WO 04/018587). However, these compounds are thermally unstable andcannot be evaporated without decomposition, which requires hightechnicomplexity for OLED production and thus represents a technicaldisadvantage. For high-quality applications, it is therefore desirableto have available improved emitters, in particular with respect todevice and sublimation stability and emission colour.

Overall, there is a demand in the area of functional materials forelectronic devices for alternative materials which preferably haveimproved properties.

The applications WO 2006/033563 and US 2009/0136779, inter alia,disclose triarylamine derivatives in which the individual aryl groupsare bridged to one another. The compounds are employed as hole-transportmaterials and/or as emitting materials in electronic devices.

The application WO 10/083871 discloses compounds in which aryl groupsare condensed onto a piperidine ring. The compounds are employed ashole-transport materials and/or as emitting materials in electronicdevices. Furthermore, the unpublished application DE 102009048791.3discloses bridged carbazole derivatives containing triazinyl groups. Thecompounds are preferably employed as matrix materials for phosphorescentdopants and as electron-transport materials.

However, there continues to be a need for improvement with respect tothe lifetime, efficiency and operating voltage of the devices. Inaddition, it is advantageous for the compounds to have high thermalstability and a high glass-transition temperature and to be sublimablewithout decomposition.

The invention thus relates to a compound of the formula (I)

where the following applies to the symbols and indices occurring:

-   Y is on each occurrence, identically or differently, a single bond,    BR², C(R²)₂, R²C═CR², Si(R²)₂, C═O, C═NR², O, S, SO, SO₂, PR², POR²    or NR², where at least one group Y which represents a single bond is    present;-   T¹, T², T³ are on each occurrence, identically or differently, a    single bond, BR², C(R²)₂, R²C═CR², Si(R²)₂, C═O, C═NR², O, S, SO,    SO₂, PR², POR² or NR²;-   Ph is a phenyl group, which may be substituted by one or more    radicals R¹;-   Ar¹ is an aromatic ring system having 6 to 30 aromatic ring atoms,    which may be substituted by one or more radicals R¹;-   R¹, R² are on each occurrence, identically or differently, H, D, F,    Cl, Br, I, CHO, N(R³)₂, C(═O)R³, P(═O)(R³)₂, S(═O)R³, S(═O)₂R³,    CR³═C(R³)₂, CN, NO₂, Si(R³)₃, B(OR³)₂, OSO₂R³, OH, a straight-chain    alkyl, alkoxy or thioalkyl group having 1 to 40 C atoms or a    branched or cyclic alkyl, alkoxy or thioalkyl group having 3 to 40 C    atoms or an alkenyl or alkynyl group having 2 to 40 C atoms, each of    which may be substituted by one or more radicals R³, where one or    more non-adjacent CH₂ groups may be replaced by R³C═CR³, C≡C,    Si(R³)₂, Ge(R³)₂, Sn(R³)₂, C═O, C═S, C═Se, C═NR³, P(═O)(R³), SO,    SO₂, NR³, O, S or CONR³ and where one or more H atoms may be    replaced by D, F, Cl, Br, I, CN or NO₂, or a mono- or polycyclic    aromatic or heteroaromatic ring system having 5 to 60 aromatic ring    atoms, which may in each case be substituted by one or more    non-aromatic radicals R³, or an aryloxy or heteroaryloxy group    having 5 to 60 aromatic ring atoms, which may be substituted by one    or more non-aromatic radicals R³, or a combination of these systems,    where two or more radicals R¹ and/or R² may be linked to one another    and may form a mono- or polycyclic, aliphatic or aromatic ring    system;-   R³ is on each occurrence, identically or differently, H, D, F, Cl,    Br, I, CHO, N(R⁴)₂, C(═O)R⁴, P(═O)(R⁴)₂, S(═O)R⁴, S(═O)₂R⁴,    CR⁴═C(R⁴)₂, CN, NO₂, Si(R⁴)₃, B(OR⁴)₂, OSO₂R⁴, OH, a straight-chain    alkyl, alkoxy or thioalkyl group having 1 to 40 C atoms or a    branched or cyclic alkyl, alkoxy or thioalkyl group having 3 to 40 C    atoms or an alkenyl or alkynyl group having 2 to 40 C atoms, each of    which may be substituted by one or more radicals R¹, where one or    more non-adjacent CH₂ groups may be replaced by R⁴C═CR⁴, C≡C,    Si(R⁴)₂, Ge(R⁴)₂, Sn(R⁴)₂, C═O, C═S, C═Se, C═NR⁴, P(═O)(R⁴), SO,    SO₂, NR⁴, O, S or CONR⁴ and where one or more H atoms may be    replaced by D, F, Cl, Br, I, CN or NO₂, or a mono- or polycyclic    aromatic or heteroaromatic ring system having 5 to 60 aromatic ring    atoms, which may in each case be substituted by one or more    non-aromatic radicals R⁴, or an aryloxy or heteroaryloxy group    having 5 to 60 aromatic ring atoms, which may be substituted by one    or more non-aromatic radicals R⁴, or a combination of these systems,    where two or more radicals R³ may be linked to one another and may    form a mono- or polycyclic, aliphatic or aromatic ring system;-   R⁴ is on each occurrence, identically or differently, H, D, F or an    aliphatic, aromatic and/or heteroaromatic organic radical having 1    to 20 C atoms, in which, in addition, one or more H atoms may be    replaced by D or F; two or more identical or different substituents    R⁴ here may also be linked to one another and may form a mono- or    polycyclic, aliphatic or aromatic ring system;-   n is on each occurrence, identically or differently, 0 or 1, where    the sum of the values of n is equal to 1 or 2 and where, for n=0, a    group R¹ is bonded instead of a group Y;-   m1, m2, m3 are on each occurrence, identically or differently, 0 or    1, where, for m1, m2 or m3=0, a group R¹ is bonded instead of a    group T¹, T² or T³ respectively;-   p is equal to 0 or 1;    where the following structures are excluded:

and where not more than one group R¹ which represents a group of theformula N(R³)₂, where R³ is an aryl group, may be bonded to a singletriarylamine group in formula (I).

In a preferred embodiment of the invention, the group T² in compounds ofthe formula (I) cannot represent a single bond for p=1 and m1=m3=0. In aparticularly preferred embodiment of the invention, T¹, T² and T³ dorepresent a single bond in the case where p is equal to 1 and the sum ofthe values of the indices m1, m2 and m3 is equal to 1. In a furtherparticularly preferred embodiment of the invention, the group T² in thecompounds of the formula (I) cannot represent a single bond if m1=m3=0.

The condition that not more than one group R¹ which represents a groupof the formula N(R³)₂, where R³ is an aryl group, may be bonded to asingle triarylamino group in formula (I) will be explained in greaterdetail below.

Both the left-hand moiety (formula (Ia)) and the right-hand moiety(formula (Ib)) in the structural formulae of the compounds according tothe invention represent a single triarylamino group in the sense of theabove definition.

For example, the formula indicated below in which R³ stands for an arylgroup represents compounds which do not fall within the scope of theclaims of the present application:

In the compounds represented by the generic formula shown above, twogroups N(R³)₂, where R³ is an aryl group, are bonded to a singletriarylamino group, as explained above.

The situation is the same with compounds of the following formula inwhich R³ stands for an aryl group:

By contrast, compounds of the following formula in which R³ stands foran aryl group are covered by the claims of the present application:

This is because in this case a single group N(R³)₂, where R³ stands foran aryl group, is bonded to a single triarylamino group, as explainedabove.

An aryl group in the sense of this invention contains 6 to 60 C atoms; aheteroaryl group in the sense of this invention contains 1 to 60 C atomsand at least one heteroatom, with the proviso that the sum of C atomsand heteroatoms is at least 5. The heteroatoms are preferably selectedfrom N, O and/or S. An aryl group or heteroaryl group here is taken tomean either a simple aromatic ring, i.e. benzene, or a simpleheteroaromatic ring, for example pyridine, pyrimidine, thiophene, etc.,or a condensed (fused) aryl or heteroaryl group, for examplenaphthalene, anthracene, phenanthrene, quinoline, isoquinoline,carbazole, etc.

An aromatic ring system in the sense of this invention contains 6 to 60C atoms in the ring system. A heteroaromatic ring system in the sense ofthis invention contains 5 to 60 aromatic ring atoms and at least oneheteroatom in the ring system, with the proviso that the sum of the Catoms and heteroatoms is at least 5. The heteroatoms are preferablyselected from N, O and/or S. An aromatic or heteroaromatic ring systemin the sense of this invention is intended to be taken to mean a systemwhich does not necessarily contain only aryl or heteroaryl groups, butinstead in which, in addition, a plurality of aryl or heteroaryl groupsmay be connected by a non-aromatic unit (preferably less than 10% of theatoms other than H), such as, for example, an sp³-hybridised C, N or Oatom. Thus, for example, systems such as 9,9′-spirobifluorene,9,9-diarylfluorene, triarylamine, diaryl ether, stilbene, etc., are alsointended to be taken to be aromatic ring systems in the sense of thisinvention, as are systems in which two or more aryl groups areinterrupted, for example, by a linear or cyclic alkyl, group or by asilyl group.

An aryl or heteroaryl group, which may in each case be substituted bythe above-mentioned radicals and which may be linked to the aromatic orheteroaromatic ring system via any desired positions, is taken to mean,in particular, groups derived from benzene, naphthalene, anthracene,phenanthrene, pyrene, dihydropyrene, chrysene, perylene, fluoranthene,benzanthracene, benzophenanthrene, tetracene, pentacene, benzopyrene,furan, benzofuran, isobenzofuran, dibenzofuran, thiophene,benzothiophene, isobenzothiophene, dibenzothiophene, pyrrole, indole,isoindole, carbazole, indolocarbazole, pyridine, quinoline,isoquinoline, acridine, phenanthridine, benzo-5,6-quinoline,benzo-6,7-quinoline, benzo-7,8-quinoline, phenothiazine, phenoxazine,pyrazole, indazole, imidazole, benzimidazole, naphthimidazole,phenanthrimidazole, pyridimidazole, pyrazinimidazole,quinoxalinimidazole, oxazole, benzoxazole, naphthoxazole, anthroxazole,phenanthroxazole, isoxazole, 1,2-thiazole, 1,3-thiazole, benzothiazole,pyridazine, benzopyridazine, pyrimidine, benzopyrimidine, quinoxaline,pyrazine, phenazine, naphthyridine, azacarbazole, benzocarboline,phenanthroline, 1,2,3-triazole, 1,2,4-triazole, benzotriazole,1,2,3-oxadiazole, 1,2,4-oxadiazole, 1,2,5-oxadiazole, 1,3,4-oxadiazole,1,2,3-thiadiazole, 1,2,4-thiadiazole, 1,2,5-thiadiazole,1,3,4-thiadiazole, 1,3,5-triazine, 1,2,4-triazine, 1,2,3-triazine,tetrazole, 1,2,4,5-tetrazine, 1,2,3,4-tetrazine, 1,2,3,5-tetrazine,purine, pteridine, indolizine and benzothiadiazole, or combinations ofthese groups.

An aromatic or heteroaromatic ring system having 5-60 aromatic ringatoms, which may also in each case be substituted by radicals as definedabove and which may be linked to the aromatic or heteroaromatic groupvia any desired positions, is taken to mean, in particular, groupsderived from benzene, naphthalene, anthracene, benzanthracene,phenanthrene, benzophenanthrene, pyrene, chrysene, perylene,fluoranthene, naphthacene, pentacene, benzopyrene, biphenyl,biphenylene, terphenyl, terphenylene, fluorene, indenofluorene,indenocarbazole, spirobifluorene, dihydrophenanthrene, dihydropyrene,tetrahydropyrene, cis- or transindenofluorene, truxene, isotruxene,spirotruxene, spiroisotruxene, furan, benzofuran, isobenzofuran,dibenzofuran, thiophene, benzothiophene, isobenzothiophene,dibenzothiophene, pyrrole, indole, isoindole, carbazole, pyridine,quinoline, isoquinoline, acridine, phenanthridine, benzo-5,6-quinoline,benzo-6,7-quinoline, benzo-7,8-quinoline, phenothiazine, phenoxazine,pyrazole, indazole, imidazole, benzimidazole, naphthimidazole,phenanthrimidazole, pyridimidazole, pyrazinimidazole,quinoxalinimidazole, oxazole, benzoxazole, naphthoxazole, anthroxazole,phenanthroxazole, isoxazole, 1,2-thiazole, 1,3-thiazole, benzothiazole,pyridazine, benzopyridazine, pyrimidine, benzopyrimidine, quinoxaline,1,5-diazaanthracene, 2,7-diazapyrene, 2,3-diazapyrene, 1,6-diazapyrene,1,8-diazapyrene, 4,5-diazapyrene, 4,5,9,10-tetraazaperylene, pyrazine,phenazine, phenoxazine, phenothiazine, fluorubin, naphthyridine,azacarbazole, benzocarboline, phenanthroline, 1,2,3-triazole,1,2,4-triazole, benzotriazole, 1,2,3-oxadiazole, 1,2,4-oxadiazole,1,2,5-oxadiazole, 1,3,4-oxadiazole, 1,2,3-thiadiazole,1,2,4-thiadiazole, 1,2,5-thiadiazole, 1,3,4-thiadiazole, 1,3,5-triazine,1,2,4-triazine, 1,2,3-triazine, tetrazole, 1,2,4,5-tetrazine,1,2,3,4-tetrazine, 1,2,3,5-tetrazine, purine, pteridine, indolizine andbenzothiadiazole.

For the purposes of the present invention, a straight-chain alkyl grouphaving 1 to 40 C atoms or a branched or cyclic alkyl group having 3 to40 atoms or an alkenyl or alkynyl group having 2 to 40 C atoms, inwhich, in addition individual H atoms or CH₂ groups may be substitutedby the groups mentioned above under the definition of the radicals R¹and R², is preferably taken to mean the radicals methyl, ethyl,n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, 2-methylbutyl,n-pentyl, s-pentyl, cyclopentyl, neopentyl, n-hexyl, cyclohexyl,neohexyl, n-heptyl, cycloheptyl, n-octyl, cyclooctyl, 2-ethylhexyl,trifluoromethyl, pentafluoroethyl, 2,2,2-trifluoroethyl, ethenyl,propenyl, butenyl, pentenyl, cyclopentenyl, hexenyl, cyclohexenyl,heptenyl, cycloheptenyl, octenyl, cyclooctenyl, ethynyl, propynyl,butynyl, pentynyl, hexynyl or octynyl. An alkoxy or thioalkyl grouphaving 1 to 40 C atoms is preferably taken to mean methoxy,trifluoromethoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, i-butoxy,s-butoxy, t-butoxy, n-pentoxy, s-pentoxy, 2-methylbutoxy, n-hexoxy,cyclohexyloxy, n-heptoxy, cycloheptyloxy, n-octyloxy, cyclooctyloxy,2-ethylhexyloxy, pentafluoroethoxy, 2,2,2-trifluoroethoxy, methylthio,ethyltbio, n-propylthio, i-propylthio, n-butylthio, i-butylthio,s-butylthio, t-butylthio, n-pentylthio, s-pentylthio, n-hexylthio,cyclohexylthio, n-heptylthio, cycloheptylthio, n-octylthio,cyclooctylthio, 2-ethylhexylthio, trifluoromethylthio,pentafluoroethylthio, 2,2,2-trifluoroethylthio, ethenylthio,propenylthio, butenylthio, pentenylthio, cyclopentenylthio, hexenylthio,cyclohexenylthio, heptenylthio, cycloheptenylthio, octenylthio,cyclooctenylthio, ethynylthio, propynylthio, butynylthio, pentynylthio,hexynylthio, heptynylthio or octynylthio.

It is preferred for the groups Y, if present, each to be bonded to thegroup Ph in the ortho-position to the bond to the nitrogen atom.

It is furthermore preferred for the groups T¹, T² and T³, if present,each to be bonded to Ar¹ in the ortho-position to the bond to thenitrogen atom.

In a preferred embodiment of the compounds according to the invention, amaximum of 2 groups Y which represent a single bond are present.Particularly preferably, precisely one group Y which represents a singlebond is present.

In a further preferred embodiment of the invention, the sum of thevalues of n is equal to 1.

In a particularly preferred embodiment of the invention, precisely onegroup Y represents a single bond and precisely one further group Y isselected from BR², C(R²)₂, Si(R²)₂, C═O, C═NR², O, S, SO, SO₂, PR², POR²and NR².

It is furthermore preferred for T¹, T² and T³ to be selected on eachoccurrence, identically or differently, from a single bond, C(R²)₂, C═O,O, S and NR². In this case, R² is preferably selected from H, D, astraight-chain alkyl group having 1 to 8 carbon atoms, a branched alkylgroup having 3 to 8 carbon atoms or an aryl group having 6 to 10 carbonatoms, where the said groups may each be substituted by one or moregroups R³.

T¹, T² and T³ are particularly preferably on each occurrence a singlebond. It is furthermore preferred here, in combination with the twopreferred embodiments of T¹, T² and T³ mentioned above, for T² not torepresent a single bond if p=1 and m1=m3=0.

It is furthermore preferred in accordance with the invention for

-   Y to be on each occurrence, identically or differently, a single    bond, C(R²)₂, C═O, O, S or NR², where at least one group Y which    represents a single bond is present.

In this case, R² is preferably selected from H, D, a straight-chainalkyl group having 1 to 8 carbon atoms, a branched alkyl group having 3to 8 carbon atoms or an aryl group having 6 to 10 carbon atoms, wherethe said groups may each be substituted by one or more groups R³.

In a preferred embodiment of the invention, the sum of the values of theindices m1, m2 and m3 is equal to 2.

In this case, it is preferred in accordance with the invention forprecisely one of the two groups T¹, T² and T³ to represent a single bondand for the other of the two groups T¹, T² and T³ present to represent agroup selected from the group comprising C(R²)₂, C═O, O, S or NR². Inthis case, it is furthermore preferred for the sum of the values nsimultaneously to be equal to one.

In a further preferred embodiment of the invention, the sum of thevalues of the indices m1, m2 and m3 is equal to 1. In combination withthe said preferred embodiment, it is preferred for the single group T¹,T² or T³ present in this case not to represent a single bond.

In a further preferred embodiment of the invention, all indices m1, m2and m3 are equal to zero.

R¹ is furthermore preferably not a group N(R³)₂ where R³ is an arylgroup.

R¹ is again furthermore preferably selected on each occurrence,identically or differently, from H, D, F, CN, Si(R³)₃ or astraight-chain alkyl or alkoxy group having 1 to 20 C atoms or abranched or cyclic alkyl or alkoxy group having 3 to 20 C atoms, each ofwhich may be substituted by one or more radicals R³, where one or moreadjacent or non-adjacent CH₂ groups may be replaced by —C≡C—, R³C═CR³,Si(R³)₂, C═O, C═NR³, NR³, O, S, COO or CONR³, or an aryl or heteroarylgroup having 5 to 30 aromatic ring atoms, which may in each case besubstituted by one or more radicals R³.

The radical R² is preferably selected on each occurrence, identically ordifferently, from H, D, F, CN, Si(R³)₃, N(R³)₂ or a straight-chain alkylor alkoxy group having 1 to 20 C atoms or a branched or cyclic alkyl oralkoxy group having 3 to 20 C atoms, each of which may be substituted byone or more radicals R³, where one or more adjacent or non-adjacent CH₂groups may be replaced by —C≡C—, R³C═CR³, Si(R³)₂, C═O, C═NR³, NR³, O,S, COO or CONR³, or an aryl or heteroaryl group having 5 to 30 aromaticring atoms, which may in each case be substituted by one or moreradicals R³.

R² is particularly preferably selected on each occurrence, identicallyor differently, from H, D, a straight-chain alkyl group having 1 to 8carbon atoms, a branched alkyl group having 3 to 8 carbon atoms or anaryl group having 6 to 18 carbon atoms, where the said groups may eachbe substituted by one or more groups R³. R² is very particularlypreferably equal to H, D, methyl or phenyl.

It is furthermore preferred for the compounds according to the inventionto have to contain at least one group R² which represents an aryl grouphaving 6 to 10 carbon atoms which is substituted by one or more radicalsR³.

The compounds according to the invention particularly preferably containleast one group R² which represents a phenyl group which is substitutedone or more radicals R³.

It is furthermore preferred for two or more radicals R² to form a ringwith one another. It is particularly preferred for the ring formation oftwo radicals R² to form a spiro compound. Furthermore, two radicals R²which are part of a group C(R²)₂ which stands for Y, T¹, T², T³ or Lparticularly preferably form a spiro compound. L here is as defined inone of the following sections.

It is preferred in accordance with the invention for the radicals R¹ andR² not to represent structures of the following formulae (A) to (G):

where the following applies to the symbols and indices occurring:

-   Ar² is on each occurrence, identically or differently, an aromatic    or heteroaromatic ring system having 5-30 aromatic ring atoms, which    may be substituted by one or more non-aromatic radicals R³; two    radicals Ar² here which are bonded to the same N atom or P atom may    also be linked to one another by a single bond or a bridge selected    from N(R³), C(R³)₂ or O;-   R³ is as defined above;-   p stands for 0 or 1;    and the symbol * indicates the position in which the group is    bonded.

It is furthermore preferred in accordance with the invention for theradicals R¹ and R² not to be linked to one another.

The radical R³ is preferably selected on each occurrence, identically ordifferently, from H, D, F, CN, Si(R⁴)₃, N(R⁴)₂ or a straight-chain alkylor alkoxy group having 1 to 20 C atoms or a branched or cyclic alkyl oralkoxy group having 3 to 20 C atoms, each of which may be substituted byone or more radicals R⁴, where one or more adjacent or non-adjacent CH₂groups may be replaced by —C≡C—, R⁴C═CR⁴, Si(R⁴)₂, C═O, C═NR⁴, NR⁴, O,S, COO or CONR⁴, or an aryl or heteroaryl group having 5 to 30 aromaticring atoms, which may in each case be substituted by one or moreradicals R⁴.

The compounds of the formula (I) according to the invention can also berepresented by one of the two formulae (II) and (III):

where the symbols and indices occurring are defined as indicated above.

For compounds of the formula (III), it is preferred for the group T² notto represent a single bond if m1=m3=0.

Preferred embodiments of the group Ph conform to the formulae (Ph-1) and(Ph-2):

where the bonds to the two nitrogen atoms or to the nitrogen atom and tothe group Ar¹ are represented by the dashed lines, and the symbols #mark the position of the bond to a group Y, if present, and where thestructures may be substituted in all free positions by radicals R¹ asdefined above.

Preferred embodiments of the group Ar¹ conform to the following formulae(Ar¹-1) to (Ar¹-7):

where

-   L is selected on each occurrence, identically or differently, from    BR², C(R²)₂, R²C═CR², Si(R²)₂, C═O, C═NR², O, S, SO, SO₂, PR², POR²    and NR²;    and where the bonds to the group Ph and to the nitrogen atom are    represented by the dashed lines, and the symbols # mark the position    of the bond to a group T¹, T² or T³, if present, and where the    groups may be substituted in all free positions by radicals R¹ as    defined above.

In a preferred embodiment of the invention,

-   L is selected on each occurrence, identically or differently, from    C(R²)₂, C═O, O, S and NR².

In this case, R² is preferably selected from H, D, a straight-chainalkyl group having 1 to 8 carbon atoms, a branched alkyl group having 3to 8 carbon atoms or an aryl group having 6 to 10 carbon atoms, wherethe said groups may each be substituted by one or more groups R³.

L is very particularly preferably selected on each occurrence,identically or differently, from C(R²)₂ and NR².

In this case, R² is preferably selected from H, D, a straight-chainalkyl group having 1 to 8 carbon atoms, a branched alkyl group having 3to 8 carbon atoms or an aryl group having 6 to 10 carbon atoms, wherethe said groups may each be substituted by one or more groups R³.

It is preferred in accordance with the invention for Ar¹ to represent anaromatic ring system having 6 to 20 aromatic ring atoms which issubstituted by one or more radicals R¹. Ar¹ is particularly preferablyan aromatic system having 6 to 18 aromatic ring atoms which comprisesexclusively phenyl groups and which is substituted by one or moreradicals R¹. In a particularly preferred embodiment of the invention,Ar¹ is a phenyl group which is substituted by one or more radicals R¹.

Particularly preferred embodiments of the group Ar¹ conform to thefollowing formulae (Ar¹-8) to (Ar¹-35):

where the bonds to the group Ph and to the nitrogen atom are representedby the dashed lines, and the symbols # mark the position of the bond toa group T¹, T² or T³, if present, and where the groups may besubstituted in all free positions by radicals R¹, and the groups R¹ maybe linked to one another and may thus form a further aliphatic oraromatic ring.

Particularly preferred embodiments of the compounds of the formula (I)according to the invention are represented by the following formulae(I-1) to (I-55):

where the groups L and R¹ are defined as indicated above. L in theformulae indicated above is very particularly preferably selected oneach occurrence, identically or differently, from C(R²)₂ and NR².

In this case, R² is preferably selected from H, D, a straight-chainalkyl group having 1 to 8 carbon atoms, a branched alkyl group having 3to 8 carbon atoms or an aryl group having 6 to 10 carbon atoms, wherethe said groups may each be substituted by one or more groups R³.

In general, the preferred and particularly preferred embodimentsmentioned in the present application can in accordance with theinvention be combined with one another as desired.

In particular, it is preferred for the said preferred embodiments forAr¹, R¹, Y, T¹, T², T³ and L to occur in combination with one another.

Examples of preferred compounds of the formula (I) are the structuresdepicted below.

The compounds according to the invention can be obtained by syntheticsteps known to the person skilled in the art, such as, for example,transition metal-catalysed coupling reactions and acid-catalysedring-closure reactions.

Thus, for example, a diarylamino group can be introduced byHartwig-Buchwald coupling if a halogen-substituted group Ar¹ is presentin a precursor molecule of the compounds according to the invention.

Scheme 1 below shows the synthesis of various bridged triarylamine units(A-E) which are important intermediates in the synthesis of thecompounds according to the invention.

In general, R and R¹ in the following schemes stand for a radical asdefined by R¹ and R² above.

Depending on the desired bromine substitution (A-C, Scheme 1),cyclisation can take place via the intermediate of a tertiary alcoholbefore or after the bromination of the aromatic parent structure. Ringclosure gives a divalent C(R′)₂ bridge (A-C, Scheme 1).

Suitable starting compounds for the formation of the C(R′)₂ bridge are,for example, a carboxylate group or an acetyl group, which can then beconverted into a carbon bridge in the ring-closure reaction. Alsosuitable is a phenol group or thiophenol group, which can then beconverted into an oxygen or sulfur bridge in the ring-closure reaction(D). Likewise suitable is a nitro group or amino group, which can thenbe converted into a nitrogen bridge in the ring-closure reaction (E).The divalent bridge may subsequently be substituted by further radicals,for example by alkyl or aryl groups. The bridged carbazole compoundprepared in this way can then be functionalised, for examplehalogenated, preferably brominated, in a further step.

The functionalised, in particular brominated compounds from Scheme 1represent a central unit for further functionalisation, as depicted inScheme 2.

Hartwig-Buchwald coupling to diarylamines leads directly to thecompounds according to the invention or to precursor compounds, whichcan be functionalised further. In this way, arylamino and carbazolegroups can be introduced (Scheme 2).

Alternatively, the compounds A to E can be converted intoaryl-substituted compounds by Suzuki coupling to correspondingarylboronic acids. In this way, relatively large aromatic systems can beachieved as embodiments of the groups Ar¹ in the compounds of theformula (I). This may be followed by halogenation and coupling toarylamino or carbazole groups, again giving compounds according to theinvention.

The present invention furthermore relates to a process for thepreparation of a compound of the formula (I), characterised in that atleast one ring-closure reaction for the introduction of a bridging groupY, T¹, T², T³ or L is carried out.

The ring-closure reaction can optionally be followed by a couplingreaction for the introduction of the diarylamino group. Alternatively,the said diarylamino group may already be present in the molecule beforethe introduction of the bridging groups.

The compounds according to the invention described above, in particularcompounds which are substituted by reactive leaving groups, such asbromine, iodine, boronic acid or boronic acid ester, can be used asmonomers for the preparation of corresponding oligomers, dendrimers orpolymers. The oligomerisation or polymerisation here is preferablycarried out via the halogen functionality or the boronic acidfunctionality.

The invention therefore furthermore relates to oligomers, polymers ordendrimers comprising one or more compounds of the formula (I), wherethe bond(s) to the polymer, oligomer or dendrimer may be localised atany desired positions substituted by R¹ or R² in formula (I). Dependingon the linking of the compound of the formula (I), the compound is partof a side chain of the oligomer or polymer or part of the main chain. Anoligomer in the sense of this invention is taken to mean a compoundwhich is built up from at least three monomer units. A polymer in thesense of the invention is taken to mean a compound which is built upfrom at least ten monomer units. The polymers, oligomers or dendrimersaccording to the invention may be conjugated, partially conjugated ornon-conjugated. The oligomers or polymers according to the invention maybe linear, branched or dendritic. In the structures linked in a linearmanner, the units of the formula (I) may be linked directly to oneanother or linked to one another via a diva-group, for example via asubstituted or unsubstituted alkylene group, via a heteroatom or via adivalent aromatic or heteroaromatic group. In and dendritic structures,three or more units of the formula (I) may, for example, be linked via atrivalent or polyvalent group, for example via a trivalent or polyvalentaromatic or heteroaromatic group, to give a or dendritic oligomer orpolymer.

For the recurring units of the formula (I) in oligomers, dendrimers andpolymers, the same preferences apply as described above for compounds ofthe formula (I).

For the preparation of the oligomers or polymers, the monomers accordingto the invention are homopolymerised or copolymerised with furthermonomers. Suitable and preferred comonomers are selected from fluorenes(for example in accordance with EP 842208 or WO 00/22026),spirobifluorenes (for example in accordance with EP 707020, EP 894107 orWO 06/061181), para-phenylenes (for example in accordance with WO92/18552), carbazoles (for example in accordance with WO 04/070772 or WO04/113468), thiophenes (for example in accordance with EP 1028136),dihydrophenanthrenes (for example in accordance with WO 05/014689 or WO07/006383), cis- and trans-indenofluorenes (for example in accordancewith WO 04/041901 or WO 04/113412), ketones (for example in accordancewith WO 05/040302), phenanthrenes (for example in accordance with WO05/104264 or WO 07/017066) or also a plurality of these units. Thepolymers, oligomers and dendrimers usually also contain further units,for example emitting (fluorescent or phosphorescent) units, such as, forexample, vinyltriarylamines (for example in accordance with WO07/068325) or phosphorescent metal complexes (for example in accordancewith WO 06/003000), and/or charge-transport units, in particular thosebased on triarylamines.

The polymers, oligomers and dendrimers according to the invention haveadvantageous properties, in particular long lifetimes, high efficienciesand good colour coordinates.

The polymers and oligomers according to the invention are generallyprepared by polymerisation of one or more types of monomer, at least onemonomer of which results in recurring units of the formula (I) in thepolymer. Suitable polymerisation reactions are known to the personskilled in the art and are described in the literature. Particularlysuitable and preferred polymerisation reactions which result in C—C orC—N links are the following:

(A) SUZUKI polymerisation;

(B) YAMAMOTO polymerisation;

(C) STILLE polymerisation; and

(D) HARTWIG-BUCHWALD polymerisation.

The way in which the polymerisation can be carried out by these methodsand the way in which the polymers can then be separated off from thereaction medium and purified is known to the person skilled in the artand is described in detail in the literature, for example in WO03/048225, WO 04/037887 and WO 04/037887.

The present invention thus also relates to a process for the preparationof the polymers, oligomers and dendrimers according to the invention,which is characterised in that they are prepared by SUZUKIpolymerisation, YAMAMOTO polymerisation, STILLE polymerisation orHARTWIG-BUCHWALD polymerisation. The dendrimers according to theinvention can be prepared by processes known to the person skilled inthe art or analogously thereto. Suitable processes are described in theliterature, such as, for example, in Frechet, Jean M. J.; Hawker, CraigJ., “Hyperbranched polyphenylene and hyperbranched polyesters: newsoluble, three-dimensional, reactive polymers”, Reactive & FunctionalPolymers (1995), 26(1-3), 127-36; Janssen, H. M.; Meijer, E. W., “Thesynthesis and characterization of dendritic molecules”, MaterialsScience and Technology (1999), 20 (Synthesis of Polymers), 403-458;Tomalia, Donald A., “Dendrimer molecules”, Scientific American (1995),272(5), 62-6; WO 02/067343 A1 and WO 2005/026144 A1.

The compounds of the formula (I) according to the invention are suitablefor use in electronic devices, in particular in organicelectroluminescent devices (OLEDs). Depending on the substitution, thecompounds are employed in different functions and layers.

The invention therefore furthermore relates to the use of the compoundsof the formula (I) according to the invention in electronic devices. Theelectronic devices here are preferably selected from the groupconsisting of organic integrated circuits (O-ICs), organic field-effecttransistors (O-FETs), organic thin-film transistors (O-TFTs), organiclight-emitting transistors (O-LETs), organic solar cells (O-SCs),organic optical detectors, organic photoreceptors, organic field-quenchdevices (O-FQDs), light-emitting electrochemical cells (LECs), organiclaser diodes (O-lasers) and particularly preferably organicelectroluminescent devices (OLEDs).

The invention also relates to formulations comprising at least onecompound of the formula (I) or at least one polymer, oligomer ordendrimer containing at least one unit of the formula (I) and at leastone solvent, preferably an organic solvent.

The invention still furthermore relates to electronic devices comprisingat least one compound of the formula (I). The electronic devices hereare preferably selected from the devices mentioned above. Particularpreference is given to organic electroluminescent devices comprising ananode, a cathode and at least one emitting layer, characterised in thatat least one organic layer, which may be an emitting layer, ahole-transport layer or another layer, comprises at least one compoundof the formula (I).

Apart from the cathode, anode and emitting layer, the organicelectroluminescent device may also comprise further layers. These areselected, for example, from in each case one or more hole-injectionlayers, hole-transport layers, hole-blocking layers, electron-transportlayers, electron-injection layers, electron-blocking layers,exciton-blocking layers, charge-generation layers (IDMC 2003, Taiwan;Session 21 OLED (5), T. Matsumoto, T. Nakada, J. Endo, K. Mori, N.Kawamura, A. Yokoi, J. Kido, Multiphoton Organic EL Device Having ChargeGeneration Layer) and/or organic or inorganic p/n junctions. However, itshould be pointed out that each of these layers does not necessarilyhave to be present and the choice of layers is always dependent on thecompounds used and in particular also on whether the electroluminescentdevice is fluorescent or phosphorescent.

The organic electroluminescent device may also comprise a plurality ofemitting layers. These emission layers in this case particularlypreferably have in total a plurality of emission maxima between 380 nmand 750 nm, resulting overall in white emission, i.e. various emittingcompounds which are able to fluoresce or phosphoresce and emit blue andyellow, orange or red light are used in the emitting layers. Particularpreference is given to three-layer systems, i.e. systems having threeemitting layers, where at least one of these layers comprises at leastone compound of the formula (I) and where the three layers exhibit blue,green and orange or red emission (for the basic structure see, forexample, WO 05/011013). Alternatively and/or additionally, the compoundsaccording to the invention may also be present in the hole-transportlayer. Emitters which have broadband emission bands and thus exhibitwhite emission are likewise suitable for white emission.

In a preferred embodiment of the invention, the compounds of the formula(I) are employed as hole-transport material. The compounds are thenpreferably employed in a hole-transport layer and/or in a hole-injectionlayer. A hole-injection layer in the sense of this invention is a layerwhich is directly adjacent to the anode. For the purposes of thisinvention, a hole-transport layer is a layer which is located betweenthe hole-injection layer and the emission layer. The hole-transportlayer can be directly adjacent to the emission layer. If the compoundsof the formula (I) are used as hole-transport material, it may bepreferred for them to be doped with electronacceptor compounds, forexample by F₄-TCNQ or with compounds as described in EP 1476881 or EP1596445. If the compound of the formula (I) is employed ashole-transport material in a hole-transport layer, the compound can beemployed as the pure material, i.e. in a proportion of 100%, in thehole-transport layer or it can be employed in combination with furthercompounds in the hole-transport layer.

It is preferred in accordance with the invention for the compound of theformula (I) to be employed in an electronic device comprising one ormore phosphorescent emitters. The compound here can be used in ahole-transport layer, a hole-injection layer or in the emitting layer,particularly preferably in a hole-transport layer.

In a further embodiment of the present invention, the compounds of theformula (I) are employed as matrix material for emitting materials,preferably phosphorescent dopants. In this case, it is particularlypreferred for the compounds of the formula (I) to be employed as matrixmaterial for emitting materials in an organic electroluminescent device.

In a further preferred embodiment of the invention, the organicelectroluminescent device may also comprise a plurality of emittinglayers, where at least one emitting layer comprises at least onecompound of the formula (I) and at least one emitter, preferablyphosphorescent.

The mixture comprising the compound of the formula (I) and thephosphorescent emitter which is employed in the emitting layerpreferably comprises between 99 and 50% by vol., preferably between 98and 50% by vol., particularly preferably between 97 and 60% by vol., inparticular between 95 and 85% by vol., of the compound of the formula(I), based on the entire mixture comprising emitter and matrix material.Correspondingly, the mixture comprises between 1 and 50% by vol.,preferably between 2 and 50% by vol., particularly preferably between 3and 40% by vol., in particular between 5 and 15% by vol., of thephosphorescent emitter, based on the entire mixture comprising emitterand matrix material.

A further preferred embodiment of the present invention is the use ofthe compound according to the invention as matrix material for aphosphorescent emitter in combination with a further matrix material.Particularly suitable matrix materials which can be employed incombination with the compounds according to the invention are aromaticketones, aromatic phosphine oxides or aromatic sulfoxides or sulfones,for example in accordance with WO 04/013080, WO 04/093207, WO 06/005627or the application WO 10/006680, triarylamines, carbazole derivatives,for example CBP (N,N-biscarbazolylbiphenyl) or the carbazole derivativesdisclosed in WO 05/039246, US 2005/0069729, JP 2004/288381, EP 1205527or WO 08/086851, indolocarbazole derivatives, for example in accordancewith WO 07/063754 or WO 08/056746, azacarbazole derivatives, for exampleaccordance with EP 1617710, EP 1617711, EP 1731584, bipolar matrixmaterials, for example in accordance with WO 07/137725, silanes, forexample in accordance with WO 05/111172, azaboroles or boronic esters,for example in accordance with WO 06/117052, triazine derivatives, forexample in accordance with the application WO 10/015306, WO 07/063754 orWO 08/056746, zinc complexes, for example in accordance with EP 652273or WO 09/062578, diazasilole or tetraazasilole derivatives, for examplein accordance with the application WO 10/054729, diazaphospholederivatives, for example in accordance with the application WO10/054730, or indenocarbazole derivatives, for example in accordancewith the unpublished application DE 102009023155.2.

Suitable phosphorescent compounds (=triplet emitters) are, inparticular, compounds which emit light, preferably in the visibleregion, on suitable excitation and in addition contain at least one atomhaving an atomic number greater than 20, preferably greater than 38 andless than 84, particularly preferably greater than 56 and less than 80.The phosphorescent emitters used are preferably compounds which containcopper, molybdenum, tungsten, rhenium, ruthenium, osmium, rhodium,iridium, palladium, platinum, silver, gold or europium, in particularcompounds which contain iridium or platinum.

Examples of the emitters described above are revealed by theapplications WO 00/70655, WO 01/41512, WO 02/02714, WO 02/15645, EP1191613, EP 1191612, EP 1191614, WO 05/033244, WO 05/019373 and US2005/0258742. In general, all phosphorescent complexes as used inaccordance with the prior art for phosphorescent OLEDs and as are knownto the person skilled in the art in the area of organicelectroluminescence are suitable, and the person skilled in the art willbe able to use further phosphorescent complexes without inventive step.

Examples of suitable phosphorescent emitter compounds are revealed bythe following table:

In a further embodiment of the invention, the compound of the formula(I) is employed in an interlayer between an emission layer comprising asinglet emitter compound and an emission layer comprising a tripletemitter compound. In this connection, reference is made to theapplication WO 10/115498. If the compounds according to the inventionare used in an interlayer, it is preferred for this interlayer to beemployed in an electronic device comprising three emitting layersbetween a green-emitting layer comprising a triplet emitter compound anda blue-emitting layer comprising a singlet emitter compound.

In a further preferred embodiment of the invention, the compound of theformula (I) is employed as emitting material in an emitting layer. Thecompounds of the formula (n) are particularly suitable as emittingmaterial if at least one condensed aryl or heteroaryl group or a furtherdiarylamino substituent is present in the molecule.

If the compound of the formula (I) is employed as emitting material inan emitting layer, it is preferably employed in combination with amatrix material. In a system comprising matrix and dopant, a matrixmaterial is taken to mean the component which is present in the higherproportion in the system. In a system comprising a matrix al in aplurality of dopants, the matrix is taken to mean the component whoseproportion in the mixture is the highest.

The proportion of the compound of the formula (I) in the mixture of theemitting layer is between 0.1 and 50.0% by vol., preferably between 0.5and 20.0% by vol., particularly preferably between 1.0 and 10.0% by vol.Correspondingly, the proportion of the matrix material is between 50.0and 99.9% by vol., preferably between 80.0 and 99.5% by vol.,particularly preferably between 90.0 and 99.0% by vol.

Matrix materials which are preferred in accordance with the inventionare listed in a following section.

The materials preferably employed in the electronic devices according tothe invention for the respective functions are mentioned below.

Preferred emitter materials are selected from the class of themonostyrylamines, the distyrylamines, the tristyrylamines, thetetrastyrylamines, the styrylphosphines, the styryl ethers and thearylamines. A monostyrylamine is taken to mean a compound which containsone substituted or unsubstituted styryl group and at least one,preferably aromatic, amine. A distyrylamine is taken to mean a compoundwhich contains two substituted or unsubstituted styryl groups and atleast one, preferably aromatic, amine. A tristyrylamine is taken to meana compound which contains three substituted or unsubstituted styrylgroups and at least one, preferably aromatic, amine. A tetrastyrylamineis taken to mean a compound which contains four substituted orunsubstituted styryl groups and at least one, preferably aromatic,amine. The styryl groups are particularly preferably stilbenes, whichmay also be further substituted. Corresponding phosphines and ethers aredefined analogously to the amines. An arylamine or aromatic amine in thesense of this invention is taken to mean a compound which contains threesubstituted or unsubstituted aromatic or heteroaromatic ring systemsbonded directly to the nitrogen. At least one of these aromatic orheteroaromatic ring systems is preferably a condensed ring system,particularly preferably having at least 14 aromatic ring atoms.Preferred examples thereof are aromatic anthracenamines, aromaticanthracenediamines, aromatic pyrenamines, aromatic pyrenediamines,aromatic chrysenamines or aromatic chrysenediamines. An aromaticanthracenamine is taken to mean a compound in which one diarylaminogroup is bonded directly to an anthracene group, preferably in the9-position. An aromatic anthracenediamine is taken to mean a compound inwhich two diarylamino groups are bonded directly to an anthracene group,preferably in the 9,10-position. Aromatic pyrenamines, pyrenediamines,chrysenamines and chrysenediamines are defined analogously thereto,where the diarylamino groups are preferably bonded to the pyrene in the1-position or in the 1,6-position. Further preferred emitter materialsare selected from indenofluorenamines or indenofluorenediamines, forexample in accordance with WO 06/122630, benzoindenofluorenamines orbenzoindenofluorenediamines, for example in accordance with WO08/006449, and dibenzoindenoamines or dibenzoindenofluorenediamines, forexample in accordance with WO 07/140847. Examples of emitter materialsfrom the class of the styrylamines are substituted or unsubstitutedtristilbenamines or the emitter materials described in WO 06/000388, WO06/058737, WO 06/000389, WO 07/065549 and WO 07/115610. Preference isfurthermore given to the condensed hydrocarbons disclosed in theapplication WO 10/012328.

Preferred emitter materials are furthermore the compounds of the formula(I) according to the invention.

Suitable emitter materials are furthermore the structures depicted inthe following table, and the derivatives of these structures disclosedin JP 06/001973, WO 04/047499, WO 06/098080, WO 07/065678, US2005/096044 and WO 04/092111.

Suitable matrix materials in the electronic devices according to theinvention are materials from various classes of substance. Preferredmatrix materials are selected from the classes of the oligoarylenes (forexample 2,2′,7,7′-tetraphenylspirobifluorene in accordance with EP676461 or dinaphthylanthracene), in particular the oligoarylenescontaining condensed aromatic groups, the oligoarylenevinylenes (forexample DPVBi or spiro-DPVBi in accordance with EP 676461), thepolypodal metal complexes (for example in accordance with WO 04/081017),the hole-conducting compounds (for example in accordance with WO04/058911), the electron-conducting compounds, in particular ketones,phosphine oxides, sulfoxides, etc. (for example in accordance with WO05/084081 and WO 05/084082), the atropisomers (for example in accordancewith WO 06/048268), the boronic acid derivatives (for example inaccordance with WO 06/117052) or the benzanthracenes (for example inaccordance with WO 08/145239). Suitable matrix materials are furthermorealso the compounds according to the invention. Apart from the compoundsaccording to the invention, particularly preferred matrix materials areselected from the classes of the oligoarylenes, comprising naphthalene,anthracene, benzanthracene and/or pyrene or atropisomers of thesecompounds, the oligoarylenevinylenes, the ketones, the phosphine oxidesand the sulfoxides. Apart from the compounds according to the invention,very particularly preferred matrix materials are selected from theclasses of the oligoarylenes, comprising anthracene, benzanthracene,benzophenanthrene and/or pyrene or atropisomers of these compounds. Anoligoarylene in the sense of this invention is intended to be taken tomean a compound in which at least three aryl or arylene groups arebonded to one another.

Suitable matrix materials are, for example, the materials depicted inthe following table, and derivatives of these materials, as disclosed inWO 04/018587, WO 08/006449, U.S. Pat. No. 5,935,721, US 2005/0181232, JP2000/273056, EP 681019, US 2004/0247937 and US 2005/0211958.

Suitable charge-transport materials, as can be used in thehole-injection or hole-transport layer or in the electron-transportlayer of the organic electroluminescent device according to theinvention, are, for example, the compounds disclosed in Y. Shirota etal., Chem. Rev. 2007, 107(4), 953-1010, or other materials as areemployed in these layers in accordance with the prior art.

The cathode of the organic electroluminescent device preferablycommetals having a low work function, metal alloys or multilayeredstructures comprising various metals, such as, for example,alkaline-earth metals, alkali metals, main-group metals or lanthanoids(for example Ca, Ba, Mg, Al, In, Mg, Yb, Sm, etc.). Also suitable arealloys comprising an alkali metal or alkaline-earth metal and silver,for example an alloy comprising magnesium and silver. In the case ofmultilayered structures, further which have a relatively high workfunction, such as, for example, Ag or Al, can also be used in additionto the said metals, in which case of the metals, such as, for example,Ca/Ag or Ba/Ag, are generally used. It may also be preferred tointroduce a thin interlayer of a material having a high dielectricconstant between a metallic cathode and the organic semiconductor.Suitable for this purpose are, for example, alkali metal fluorides oralkaline-earth metal fluorides, but also the corresponding oxides orcarbonates (for example LiF, Li₂O, BaF₂, MgO, NaF, CsF, Cs₂CO₃, etc.).Furthermore, lithium quinolinate (LiQ) can be used for this purpose. Thelayer thickness of this layer is preferably between 0.5 and 5 nm.

The anode preferably comprises materials having a high work function.The anode preferably has a work function of greater than 4.5 eV vs.vacuum. Suitable for this purpose are on the one hand metals having ahigh redox potential, such as, for example, Ag, Pt or Au. On the otherhand, metal/metal oxide electrodes (for example Al/Ni/NiO_(x),Al/PtO_(x)) may also be preferred. For some applications, at least oneof the electrodes must be transparent in order to facilitate eitherirradiation of the organic material (organic solar cells) or thecoupling-out of light (OLEDs, O-lasers). A preferred structure uses atransparent anode. Preferred anode materials here are conductive mixedmetal oxides. Particular preference is given to indium tin oxide (ITO)or indium zinc oxide (IZO). Preference is furthermore given toconductive, doped organic materials, in particular conductive, dopedpolymers.

The device is appropriately (depending on the application) structured,provided with contacts and finally sealed, since the lifetime of thedevices according to the invention is shortened in the presence of waterand/or air.

In a preferred embodiment, the organic electroluminescent deviceaccording to the invention is characterised in that one or more layersare applied by means of a sublimation process, in which the materialsare applied by vapour deposition in vacuum sublimation units at aninitial pressure of less than 10⁻⁵ mbar, preferably less than 10⁻⁶ mbar.However, it is also possible here for the initial pressure to be evenlower, for example less than 10⁻⁷ mbar.

Preference is likewise given to an organic electroluminescent device,characterised in that one or more layers are applied by means of theOVPD (organic vapour phase deposition) process or with the aid ofcarrier-gas sublimation, in which the materials are applied at apressure of between 10⁻⁵ mbar and 1 bar. A special case of this processis the OVJP (organic vapour jet printing) process, in which thematerials are applied directly through a nozzle and are thus structured(for example M. S. Arnold et al., Appl. Phys. Lett. 2008, 92, 053301).

Preference is furthermore given to an organic electroluminescent device,characterised in that one or more layers are produced from solution,such as, for example, by spin coating, or by means of any desiredprinting process, such as, for example, screen printing, flexographicprinting, nozzle printing or offset printing, but particularlypreferably LITI (light induced thermal imaging, thermal transferprinting) or ink-jet printing. Soluble compounds of the formula (I) arenecessary for this purpose. High solubility can be achieved throughsuitable substitution of the compounds.

For the production of an organic electroluminescent device according tothe invention, it is furthermore preferred to apply one or more layersfrom solution and one or more layers by a sublimation process.

In accordance with the invention, the electronic devices comprising oneor more compounds of the formula (I) can be employed in displays, aslight sources in lighting applications and as light sources in medicaland/or cosmetic applications (for example light therapy).

The compounds according to the invention have excellent hole mobilityand are therefore very highly suitable as hole-transport materials. Thehigh hole mobility enables a reduction in the operating voltage and animprovement in the operating lifetime of the electronic devicescomprising the compounds according to the invention. Furthermore, thecompounds according to the invention, on use in electronic devices,result in higher power efficiency of the devices.

Furthermore, the compounds of the formula (I) are distinguished by highoxidation stability in solution, which has an advantageous effect duringpurification and handling of the compounds and on use thereof inelectronic devices.

The compounds are furthermore highly suitable for use as matrixmaterials in mixed-matrix systems, where they preferably result in areduction in the operating voltage and an increase in the lifetime ofthe electronic devices.

Furthermore, the compounds of the formula (I) are temperature-stable andcan thus be sublimed substantially without decomposition. Purificationof the compounds is thus simplified, and the compounds can be obtainedin higher purity, which has a positive effect on the performance data ofthe electronic devices comprising the materials. In particular, deviceshaving longer operating lifetimes can thus be produced.

The invention is explained in greater detail by the following workingexamples, without wishing it to be restricted thereby.

WORKING EXAMPLES A) Syntheses of Compounds According to the Invention inAccordance with Examples 1 to 30

The following syntheses are carried out, unless indicated otherwise,under a protective-gas atmosphere. The starting materials can bepurchased from ALDRICH or ABCR (palladium(II) acetate,tri-o-tolylphosphine, inorganics, solvents). The synthesis of8,8-dimethylindolo[3,2,1-de]acridine and7,7,11,11-tetramethyl-7H,11H-benz[1,8]indolo[2,3,4,5,6-de]acridine canbe carried out in accordance with the literature (Chemische Berichte1980, 113 (1), 358-84). The syntheses of 8H-indolo[3,2,1-de]phenazine(Journal of the Chemical Society 1958, 4492-4) andB-[4-(1-phenyl-1H-benzimidazol-2-yl)phenyl]boronic acid (AdvancedFunctional Materials 2008, 18 (4), 584-590),2-bromoindolo[3,2,1-jk]carbazole and indolo[3,2,1-jk]carbazoleboronicacid (Chemistry A European Journal, 2009, 15 (22), 5482-5490),N-[1,1′-biphenyl]-4-yl-9,9-dimethyl-9H-fluoren-2-amine (WO 2006073054)and7-bromo-2,12-dimethyl-10-phenyl-10,12-dihydro-10-azaindeno[2,1-b]fluorene(see as yet unpublished application DE 102009023155.2) are likewiseknown from the literature.

Example 1: 3-Bromo-8,8-dimethyl-8H-Indolo[3,2,1-de]acridine

Methyl 2-(3-bromo-9H-carbazole)benzoate

62 g (207 mmol) of methyl 2-(9H-carbazole)benzoate are cooled to −10° C.in 2000 ml of DMF, 37.3 g (207 mmol) of NBS are added in portions, andthe mixture is stirred at room temperature for 6 h. 500 ml of water aresubsequently added to the mixture, which Is then extracted with CH₂Cl₂.The organic phase is dried over MgSO₄, and the solvent is removed invacuo.

The product is washed by stirring with hot toluene and filtered off withsuction.

Yield: 72 g (190 mmol), 92% of theory, purity according to ¹H-NMR about98%.

2-[2-(3-Bromocarbazol-9-yl)phenyl]propan-2-ol

81 g (213 mmol) of methyl 2-(3-bromo-9H-carbazole)benzoate are dissolvedin 1500 ml of dried THF and degassed. The mixture is cooled to −78° C.,and 569 ml (854 mmol) of methyllithium are added over the course of 40min. The mixture is allowed to warm to −40° C. over the course of 1 h,and the reaction is monitored by TLC. When the reaction is complete, itis carefully quenched at −30° C. using MeOH. The reaction solution isevaporated to ⅓, and 1 l of CH₂Cl₂ is added, the mixture is washed, andthe organic phase is dried over MgSO₄ and evaporated.

Yield: 73 g (193 mmol), 91% of theory, purity according to ¹H-NMR about94%.

6-Bromo-8,8-dimethyl-8H-indolo[3,2,1-de]acridine

16.3 g (44 mmol) of 2-[2-(3-bromocarbazol-9-yl)phenyl]propan-2-ol aredissolved in 1200 ml of degassed toluene, a suspension of 40 g ofpolyphosphoric acid and 28 ml of methanesulfonic acid is added, and themixture is heated at 60° C. for 1 h. The batch is cooled, and water isadded. A solid precipitates out and is dissolved in CH₂Cl₂/THF (1:1).The solution is carefully rendered alkaline using 20% NaOH, and thephases are separated and dried over MgSO₄. The solid obtained is washedby stirring with heptane. Yield: 13.5 g (37 mmol), 87% of theory, purityaccording to ¹H-NMR about 95%.

Example 2: 6-Bromo-8,8-dimethyl-3-phenyl-8H-lndolo[3,2,1-de]-acridine

Methyl 2-(3-phenyl-9H-carbazole)benzoate

85 g (350 mmol) of 3-phenyl-9H-carbazole, 63 ml (262 mmol) of methyl2-iodobenzoate, 87 g (631 mmol) of potassium carbonate and 9.3 g (35mmol) of 18-crown-6 are initially introduced in 1200 ml of DMF under aprotective gas and heated at 130° C. for 86 h. The mixture issubsequently evaporated, washed by stirring with hot heptane andpurified by chromatography (heptane/CH₂Cl₂ 1:1). The product is washedby stirring with hot hexane and filtered off with suction.

Yield: 82 g (219 mmol), 62% of theory, purity according to ¹H-NMR about97%.

Methyl 2-(3-bromo-6-phenyl-9H-carbazole)benzoate

78.4 g (207 mmol) of methyl 2-(3-phenyl-9H-carbazole)benzoate are cooledto −10° C. in 2000 ml of DMF, 37.3 g (207 mmol) of NBS are added inportions, and the mixture is stirred at room temperature for 6 h. 500 mlof water are subsequently added to the mixture, which is then extractedwith CH₂Cl₂. The organic phase is dried over MgSO₄, and the solvent isremoved in vacuo. The product is washed by stirring with hot toluene andfiltered off with suction.

Yield: 91.4 g (200 mmol), 95% of theory, purity according to ¹H-NMRabout 98%.

2-[2-(3-Bromo-6-phenylcarbazol-9-yl)phenyl]propan-2-ol

97 g (213 mmol) of methyl 2-(3-bromo-6-phenyl-9H-carbazole)benzoate aredissolved in 1500 ml of dried THF and degassed. The mixture is cooled to−78° C., and 569 ml (854 mmol) of methyllithium are added over thecourse of 40 min. The mixture is allowed to warm to −40° C. over thecourse of 1 h, and the reaction is monitored by TLC. When the reactionis complete, it is carefully quenched at −30° C. using MeOH. Thereaction solution is evaporated to ⅓, and 1 l of CH₂Cl₂ is added, themixture is washed, and the organic phase is dried over MgSO₄ andevaporated.

Yield: 93.4 g (204 mmol), 96% of theory, purity according to ¹H-NMRabout 96%.

6-Bromo-8,8-dimethyl-3-phenyl-8H-indolo[3,2,1-de]acridine

20 g (43.6 mmol) of2-[2-(3-bromo-6-phenylcarbazol-9-yl)phenyl]propan-2-ol are dissolved in1200 ml of degassed toluene, a suspension of 40 g of polyphosphoric acidand 28 ml of methanesuffonic acid is added, and the mixture is heated at60° C. for 1 h. The batch is cooled, and water is added. A solidprecipitates out and is dissolved in CH₂Cl₂/THF (1:1). The solution iscarefully rendered alkaline using 20% NaOH, and the phases are separatedand dried over MgSO₄. The solid obtained is washed by stirring withheptane. Yield: 16.3 g (37 mmol), 84% of theory, purity according to¹H-NMR about 95%.

Example 3: 3-Bromo-8,8-dimethyl-8H-indolo[3,2,1-de]acridine

6.3 g (22.2 mmol) of 8,8-dimethylindolo[3,2,1-de]acridine are initiallyintroduced in 150 ml of CH₂Cl₂. A solution of 3.9 g (22.3 mmol) of NBSin 100 ml of acetonitrile is subsequently added dropwise at −15° C. withexclusion of light, and the mixture is stirred at room temperature for afurther 4 h. For work-up, 150 ml of water are added to the mixture,which is then extracted with CH₂C₂. The organic phase is dried overMgSO₄, and the solvent is removed in vacuo. The product is washed bystirring with hot hexane and filtered off with suction.

Yield: 4.5 g (12 mmol), 57% of theory, purity according to ¹H-NMR about97%.

Example 4: 3,6-Dibromo-8,8-dimethyl-8H-indolo[3,2,1-de]acridine

6.3 g (22.2 mmol) of 8,8-dimethylindolo[3,2,1-de]acridine are initiallyintroduced in 150 ml of CH₂Cl₂. A solution of 8 g (45.1 mmol) of NBS in100 ml of acetonitrile is subsequently added dropwise at −15° C. withexclusion of light, and the mixture is stirred at room temperature for afurther 4 h. For work-up, 150 ml of water are added to the mixture,which is then extracted with CH₂Cl₂. The organic phase is dried overMgSO₄, and the solvents are removed in vacuo. The product is washed bystirring with hot hexane and filtered off with suction.

Yield: 7.3 g (16 mmol), 75% of theory, purity according to ¹H-NMR about97%.

Example 5:10-Bromo-8,8-dimethyl-3,6-diphenyl-8H-indolo[3,2,1-de]-acridine

8,8-Dimethyl-3,6-diphenyl-8H-indolo[3,2,1-de]acridine

19.8 g (45 mmol) of3,6-dibromo-8,8-dimethyl-8H-indolo[3,2,1-de]acridine, 11.4 g (94 mmol)of phenylboronic acid and 164 ml of saturated NaHCO₃ solution aresuspended in 1500 ml of toluene and 150 ml of ethanol. 1.9 g (1.6 mmol)of Pd(PPh₃)₄ are added to this suspension, and the reaction mixture isheated under reflux for 16 h. After cooling, the organic phase isseparated off, filtered through silica gel, washed three times with 200ml of water and subsequently evaporated to dryness.

Yield: 18.5 g (42 mmol), 95% of theory, purity according to ¹H-NMR about98%.

10-Bromo-8,8-dimethyl-3,6-diphenyl-8H-indolo[3,2,1-de]acridine

9.6 g (22.2 mmol) of8,8-dimethyl-3,6-diphenyl-8H-indolo[3,2,1-de]acridine are initiallyIntroduced in 150 ml of CH₂Cl₂. A solution of 3.9 g (22.3 mmol) of NBSin 100 ml of acetonitrile is subsequently added dropwise at −15° C. withexclusion of light, and the mixture is stirred at room temperature for afurther 4 h. For work-up, 150 ml of water are added to the mixture,which is then extracted with CH₂Cl₂. The organic phase is dried overMgSO₄, and the solvent is removed in vacuo. The product is washed bystirring with hot hexane and filtered off with suction.

Yield: 10.7 g (20.8 mmol), 94% of theory, purity according to ¹H-NMRabout 97%.

Example 6: 3-Bromo-8H-8,12b-diazabenzo[a]aceanthrylene

Fluoro-9-(2-nitrophenyl)-9H-carbazole

A degassed solution of 97 ml (990 mmol) of 2-fluoroaniline and 165 g(862 mmol) of 2-bromochlorobenzene in 1000 ml of NMP is saturated withN₂ for 1 h. Then firstly 28.9 g (100 mmol) of trichlorohexylphosphine,then 11.2 g (50 mmol) of palladium(II) acetate are added to thesolution, and 549 g (2.5 mol) of potassium carbonate in the solid stateare subsequently added. The reaction mixture is heated under reflux for18 h. After cooling to room temperature, 1000 ml of water are carefullyadded. The organic phase is washed with 4×50 ml of water and dried overMgSO₄, and the solvent is removed in vacuo. The pure product is obtainedby recrystallisation.

Yield: 111 g (760 mmol), 70% of theory, purity according to ¹H-NMR about98%.

6-Bromo-1-fluoro-9-(2-nitrophenyl)-9H-carbazole

6.7 g (22.2 mmol) of fluoro-9-(2-nitrophenyl)-9H-carbazole are initiallyduced in 150 ml of CH₂Cl₂. A solution of 3.9 g (22.3 mmol) of NBS in 100ml of acetonitrile is subsequently added dropwise at −15° C. withexclusion of light, and the mixture is stirred at room temperature for afurther 4 h. For work-up, 150 ml of water are added to the mixture,which is then extracted with CH₂Cl₂. The organic phase is dried overMgSO₄, and the solvent is removed in vacuo. The product is washed bystirring with hot hexane and filtered off with suction.

Yield: 8 g (20 mmol), 97% of theory, purity according to ¹H-NMR about97%.

2-(6-Bromo-1-fluorocarbazol-9-yl)phenylamine

67 g (219 mmol) of 6-bromo-1-fluoro-9-(2-nitrophenyl)-9H-carbazole aredissolved in 820 ml of EtOH, 143 g (755 mmol) of ZnCl₂ are added at roomtemperature, and the mixture is heated under reflux for 6 h. The mixtureis subsequently warmed to room temperature over the course of 1 h, 20%NaOH is added, and, after phase separation, the solvent is removed, andthe residue is purified by chromatography.

Yield: 44 g (125 mmol), 72% of theory, purity according to ¹H-NMR about97%.

3-Bromo-8H-8,12b-diazabenzo[a]aceanthrylene

25 g (72 mmol) of 2-(6-bromo-1-fluorocarbazol-9-yl)phenylamine aredissolved in 200 ml of DMF under a protective gas, 2.8 g (72 mmol) ofNaH (60% in oil) are added at room temperature, and the mixture isboiled under reflux for 6 h. The mixture is subsequently warmed to roomtemperature over the course of 1 h, the solvent is removed, and theresidue is purified by chromatography.

Yield: 19 g (54 mmol), 78% of theory, purity according to ¹H-NMR about98%.

Bromo-8-phenyl-8H-8,12b-diazabenzo[a]aceanthrylene

A degassed solution of 30 g (86.6 mmol) of3-bromo-8H-8,12b-diazabenzo[a]aceanthrylene and 8.8 g (95.9 mmol) ofphenylamine in 1000 ml dioxane is saturated with N₂ for 1 h. Thenfirstly 0.9 ml (4.3 mmol) of P(tBu)₃, then 0.48 g (2.1 mmol) ofpalladium(II) acetate are added to the solution, and 12.6 g (131 mmol)of NaOtBu in the solid state are subsequently added. The reactionmixture is heated under reflux for 18 h. After cooling to roomtemperature, 1000 ml of water are carefully added. The organic phase iswashed with 4×50 ml of water and dried over MgSO₄, and the solvent isremoved in vacuo. The pure product is obtained by recrystallisation.

Yield: 27 g (64 mmol), 76% of theory, purity according to ¹H-NMR about98%.

Example 7: 8,8-Dimethyl-8H-indolo[3,2,1-de]acridine-3-boronic acid

93.9 g (259 mmol) of 3-bromo-8,8-dimethyl-8H-indolo[3,2,1-de]acridineare dissolved in 1500 ml of dry THF, 135 ml (337 mmol) of a 2.5 Msolution of n-butyllithium in cyclohexane are added dropwise at −70° C.,after 1 h 37 ml of trimethyl borate (336 mmol) are added dropwise, themixture is warmed to room temperature over the course of 1 h, thesolvent is removed, and the residue, which is uniform according to¹H-NMR, is employed in the subsequent reaction without furtherpurification.

Yield: 77 g (235 mmol), 91% of theory, purity according to ¹H-NMR about98%.

Example 8: 8,8-Dimethyl-8H-indolo[3,2,1-de]acridine-6-boronic acid

93.7 g (259 mmol) of 6-bromo-8,8-dimethyl-8H-indolo[3,2,1-de]acridineare dissolved in 1500 ml of dry THF, 135 ml (337 mmol) of a 2.5 Msolution of n-butyllithium in cyclohexane are added dropwise at −70° C.,after 1 h 37 ml of trimethyl borate (336 mmol) are added dropwise, themixture is warmed to room temperature over the course of 1 h, thesolvent is removed, and the residue, which is uniform according to¹H-NMR, is employed in the subsequent reaction without furtherpurification.

Yield: 67 g (204 mmol), 80% of theory, purity according to ¹H-NMR about96%.

Example 9: 8,8-Dimethyl-6-phenyl-8H-indolo[3,2,1-de]acridine-3-boronicacid

113.4 g (259 mmol) of6-bromo-8,8-dimethyl-3-phenyl-8H-indolo[3,2,1-de]-acridine are dissolvedin 1500 ml of dry THF, 135 ml (337 mmol) of a 2.5 M solution ofn-butyllithium in cyclohexane are added dropwise at −70° C., after 1 h37 ml of trimethyl borate (336 mmol) are added dropwise, the mixture iswarmed to room temperature over the course of 1 h, the solvent isremoved, and the residue, which is uniform according to ¹H-NMR, isemployed in the subsequent reaction without further purification.

Yield: 92 g (229 mmol), 89% of theory, purity according to ¹H-NMR about98%.

Example 10:8,8-Dimethyl-3,6-diphenyl-8H-indolo[3,2,1-de]acridine-10-boronic

133 g (259 mmol) of10-bromo-8,8-dimethyl-3,6-diphenyl-8H-indolo[3,2,1-de]acridine aredissolved in 1500 ml of dry THF, 135 ml (337 mmol) of a 2.5 M solutionof n-butyllithium in cyclohexane are added dropwise at −70° C., after 1h 37 ml of trimethyl borate (336 mmol) are added dropwise, the mixtureis warmed to room temperature over the course of 1 h, the solvent isremoved, and the residue, which is uniform according to ¹H-NMR, isemployed in the subsequent reaction without further purification.

Yield: 111 g (233 mmol), 90% of theory, purity according to ¹H-NMR about98%.

Example 11:8,8-Dimethyl-3-(9-phenyl-9H-carbazol-3-yl)-8H-indolo-[3,2,1-de]acridine(compound H5)

36 g (110 mmol) of 8,8-dimethyl-8H-indolo[3,2,1-de]acridine-3-boronicacid, 35 g (110 mmol) of 3-bromo-9-phenyl-9H-carbazole and 9.7 g (92mmol) of sodium carbonate are suspended in 350 ml of toluene, of dioxaneand 500 ml of water. 913 mg (3.0 mmol) of tri-o-tolylphosphine and 112mg (0.5 mmol) of palladium(II) acetate are added to this suspension, andthe reaction mixture is heated under reflux for 16 h. After cooling, theorganic phase is separated off, filtered through silica gel, washedthree times with 200 ml of water and subsequently evaporated to dryness.The residue is recrystallised from toluene and from CH₂Cl₂/isopanol andfinally sublimed in a high vacuum.

Yield: 52 g (100 mmol), 91% of theory, purity according to HPLC 99.9%.

Example 12:4-(8,8-Dimethyl-8H-indolo[3,2,1-de]acridin-3-yl)phenyl]-diphenylamine(compound HTM2)

The compound is synthesised by the same procedure as Example 13 byreaction of the corresponding indolo[3,2,1-de]acridineboronic acid with35.6 g (110 mmol) of 4-bromophenyldiphenylamine.

The residue is recrystallised from toluene and from CH₂Cl₂/isopropanoland finally sublimed in a high vacuum.

Yield: 51 g (97 mmol), 89% of theory, purity according to HPLC 99.9%.

Example 13:8,8,8′,8′-Tetramethyl-8H,8′H-[3,3′]bi(indolo[3,2,1-de]-acridinyl)(compound H7)

The compound is synthesised by the same procedure as Example 13 byreaction of the corresponding indolo[3,2,1-de]acridineboronic acid with39 g (110 mmol) of 3-bromo-8,8-dimethyl-8H-indolo[3,2,1-de]acridine. Theresidue is recrystallised from toluene and from CH₂Cl₂/isopropanol andfinally sublimed in a high vacuum.

Yield: 55 g (100 mmol), 92% of theory, purity according to HPLC 99.9%.

Example 14:8,8,8′,8′-Tetramethyl-8H,8′H-[3,6′]bi(indolo[3,2,1-de]-acridinyl)(compound H8)

The compound is synthesised by the same procedure as Example 13 byreaction of the corresponding indolo[3,2,1-de]acridineboronic acid with39 g (110 mmol) of 6-bromo-8,8-dimethyl-8H-lndolo[3,2,1-de]acridine.

The residue is recrystallised from toluene and from CH₂Cl₂/isopropanoland finally sublimed in a high vacuum.

Yield: 49.5 g (90 mmol), 82% of theory, purity according to HPLC 99.9%.

Example 15: (8,8-Dimethyl-8H-indolo[3,2,1-de]acridin-3-yl)diphenylamine(compound HTM4)

A degassed solution of 31 g (86.6 mmol) of3-bromo-8,8-dimethyl-8H-indolo[3,2,1-de]acridine and 16 g (95.9 mmol) ofdiphenylamine in 1000 ml of dioxane is saturated with N₂ for 1 h. Thenfirstly 0.9 ml (4.3 mmol) of P(tBu)₃, then 0.48 g (2.1 mmol) ofpalladium(II) acetate are added to the solution, and 12.6 g (131 mmol)of NaOtBu in the solid state are subsequently added. The reactionmixture is heated under reflux for 18 h. After cooling to roomtemperature, 1000 ml of water are carefully added. The organic phase iswashed with 4×50 ml of water and dried over MgSO₄, and the solvent isremoved in vacuo. The pure product is obtained by recrystallisation andfinal sublimation.

Yield: 34 g (76 mmol), 89% of theory, purity according to HPLC 99.9%.

Example 16:3-(9,9-Dimethyl-9H-acridin-10-yl)-8,8-dimethyl-8H-lndolo[3,2,1-de]acridine(compound HTM5)

The compound is synthesised by the same procedure as Example 18 byreaction of 31 g (86.6 mmol) of3-bromo-8,8-dimethyl-8H-indolo[3,2,1-de]-acridine and 20 g (95.9 mmol)of 9,9′-dimethyl-9,10-dihydroacridine.

The residue is recrystallised from toluene and finally sublimed in ahigh vacuum.

Yield: 37 g (76 mmol), 80% of theory, purity according to HPLC 99.9%.

Example 17:(8,8-Dimethyl-6-phenyl-8H-indolo[3,2,1-de]acridin-3-yl)diphenylamine(compound HTM6)

The compound is synthesised by the same procedure as Example 18 byreaction of 37.6 g (86.6 mmol) of6-bromo-8,8-dimethyl-3-phenyl-8H-indolo[3,2,1-de]acridine with thecorresponding amine.

The residue is recrystallised from toluene and finally sublimed in ahigh vacuum.

Yield: 39 g (79 mmol), 87% of theory, purity according to HPLC 99.9%.

Example 18:(8,8-Dimethyl-3,6-diphenyl-8H-indolo[3,2,1-de]acridin-10-yl)diphenylamine(compound HTM7)

The compound is synthesised by the same procedure as Example 18 byreaction of 44 g (86.6 mmol) of10-bromo-8,8-dimethyl-3,6-diphenyl-8H-indolo[3,2,1-de]acridine with thecorresponding amine.

The residue is recrystallised from toluene and finally sublimed in ahigh vacuum.

Yield: 39 g (64 mmol), 75% of theory, purity according to HPLC 99.9%.

Example 19: 3-Carbazol-9-yl-8,8-dimethyl-8H-indolo[3,2,1-de]acridinecompound H9)

The compound is synthesised by the same procedure as Example 18 byreaction of 31 g (86.0 mmol) of3-bromo-8,8-dimethyl-8H-indolo[3,2,1-de]-acridine with 16 g (95.9 mmol)of carbazole.

The residue is recrystallised from toluene and finally sublimed in ahigh vacuum.

Yield: 38 g (64 mmol), 85% of theory, purity according to HPLC 99.9%.

Example 20:8-Carbazol-9-yl-2-eth-(E)-ylidene-3-phenyl-1-prop-2-en-(E)-ylidene-2,3-dihydro-1H-pyrazino[3,2,1-jk]carbazole(compound HTM9)

The compound is synthesised by the same procedure as Example 18 byreaction of 37 g (86.6 mmol) of3-bromo-8H-8,12b-diazabenzo[a]aceanthrylene with 16 g (95.9 mmol) ofcarbazole.

The residue is recrystallised from toluene and finally sublimed in ahigh vacuum.

Yield: 31 g (60 mmol), 70% of theory, purity according to HPLC 99.9%.

Example 21:N4,N4′-Bis-(8,8-dimethyl-8H-Indolo[3,2,1-de]acridin-3-yl)-N4,N4′-diphenylbiphenyl-4,4′-diamine(compound HTM8)

A degassed solution of 31 g (86.6 mmol) of3-bromo-8,8-dimethyl-8H-indolo[3,2,1-de]acridine and 13.4 g (40 mmol) ofN,N′-diphenylbenzidine in 1000 ml of dioxane is saturated with N₂ for 1h. Then firstly 0.9 ml (4.3 mmol) of P(tBu)₃, then 0.48 g (2.1 mmol) ofpalladium(II) acetate are added to the solution, and 12.6 g (131 mmol)of NaOtBu in the solid state are subsequently added. The reactionmixture is heated under reflux for 18 h. After cooling to roomtemperature, 1000 ml of water are carefully added. The organic phase iswashed with 4×50 ml of H₂O and dried over MgSO₄, and the solvent isremoved in vacuo. The pure product is obtained by recrystallisation.

Yield: 29 g (32 mmol), 81% of theory, purity according to HPLC 99.9%.

Example 22:Biphenyl-4-yl-(9,9-dimethyl-9H-fluoren-2-yl)-[4-(8,8-dimethyl-8H-indolo[3,2,1-de]acridin-3-yl)phenyl]amine(compound HTM3)

Biphenyl-4-yl-(4-bromophenyl)-(9,9-dimethyl-9H-fluoren-2-yl)amine

A degassed solution of 490 mg (0.16 mmol) of copper(I) chloride and 906mg (5 mmol) of 1,10-phenanthroline in 100 ml of toluene is saturatedwith N₂ for 1 h and heated to 130° C. 18 g (50 mmol) ofN-[1,1′-biphenyl]-4-yl-9,9-dimethyl-9H-fluoren-2-amine and 14 g (50mmol) of 1-bromo-4-iodobenzene are subsequently added to the solution,which is then heated at 180° C. for 2 h. After cooling, 180 ml of waterare added to the mixture, the organic phase is separated off, and thesolvent is removed in vacuo. The product is recrystallised fromn-hexane.

Yield: 15 g (29 mmol), 58% of theory, purity according to ¹H-NMR about98%.

Biphenyl-4-yl-(9,9-dimethyl-9H-fluoren-2-yl)-[4-(8,8-dimethyl-8H-indolo[3,2,1-de]acridin-3-yl)phenyl]amine

The compound is synthesised by the same procedure as Example 13 byreaction of the corresponding indolo[3,2,1-de]acridineboronic acid with15 g (29 mmol) ofbiphenyl-4-yl-(4-bromophenyl)-(9,9-dimethyl-9H-fluoren-2-yl)amine.

The residue is recrystallised from ethyl acetate/heptane and finallysublimed in a high vacuum.

Yield: 14.4 g (20 mmol), 69% of theory, purity according to HPLC 99.9%.

Example 23:3-(12,12-Dimethyl-10-phenyl-10,12-dihydro-10-azaindeno[2,1-b]fluoren-7-yl)-8,8-dimethyl-8H-indolo[3,2,1-de]acridine(compound H10)

The compound is synthesised by the same procedure as Example 13 byreaction of the corresponding indolo[3,2,1-de]acridineboronic acid with48 g (110 mmol) of7-bromo-2,12-dimethyl-10-phenyl-10,12-dihydro-10-azaindeno[2,1-b]fluorene.

The residue is recrystallised from toluene and from CH₂Cl₂/isopropanoland finally sublimed in a high vacuum.

Yield: 54.5 g (85 mmol), 78% of theory, purity according to HPLC 99.9%.

Example 24:[4′-(8,12b-Diazabenzo[a]aceanthrylen-8-yl)biphenyl-4-yl]-diphenylamine(compound HTM10)

1-Fluoro-9-(2-aminophenyl)-9H-carbazole

50 g (163 mmol) of 1-fluoro-9-(2-nitrophenyl)-9H-carbazole are dissolvedin 600 ml of EtOH, 67 g (489 mmol) of ZnCl₂ are added at roomtemperature, and the mixture is heated under reflux for 6 h. The mixtureis subsequently warmed to room temperature over the course of 1 h, 20%NaOH is added, and, after phase separation, the solvent is removed, andthe residue is purified by chromatography.

Yield: 33 g (119 mmol), 73% of theory, purity according to ¹H-NMR about98%.

8H-8,12b-Diazabenzo[a]aceanthrylene

30 g (109 mmol) of 1-fluoro-9-(2-aminophenyl)-9H-carbazole are dissolvedin 200 ml of DMF under a protective gas, 4.4 g (109 mmol) of NaH (60% inoil) are added at room temperature, and the mixture is boiled underreflux for 6 h. The mixture is subsequently warmed to room temperatureover the course of 1 h, the solvent is removed, and the residue ispurified by chromatography.

Yield: 23.4 g (86 mmol), 79% of theory, purity according to ¹H-NMR about98%.

[4′-(8,12b-Diazabenzo[a]aceanthrylen-8-yl)biphenyl-4-yl]diphenylamine

A degassed solution of 35.6 g (89 mmol) of(4′-bromobiphenyl-4-yl)diphenylamine and 22.0 g (81 mmol) of8H-8,12b-diazabenzo[a]aceanthrylene in 1000 ml of dioxane is saturatedwith N₂ for 1 h. Then firstly 1.0 ml (4 mmol) of P(tBu)₃, then 0.4 g (2mmol) of palladium(II) acetate are added to the solution, and 11.7 g(122 mmol) of NaOtBu in the solid state are subsequently added. Thereaction mixture is heated under reflux for 18 h. After cooling to roomtemperature, 1000 ml of water are carefully added. The organic phase isseparated off, washed with 4×50 ml of water and dried over MgSO₄, andthe solvent is removed in vacuo. The pure product is obtained byrecrystallisation and final sublimation in a high vacuum.

Yield: 33.4 g (58 mmol), 72% of theory, purity according to HPLC 99.9%.

Example 25: 3-Bromo-8,8-diphenyl-8H-indolo[3,2,1-de]acridine

Methyl 2-(3-bromo-9H-carbazole)benzoate

62 g (207 mmol) of methyl 2-(9H-carbazole)benzoate are cooled to −10° C.in 2000 ml of DMF, 37.3 g (207 mmol) of NBS are added in portions, andthe mixture is stirred at room temperature for 6 h. 500 ml of water aresubsequently added to the mixture, which is then extracted with CH₂Cl₂.The organic phase is dried over MgSO₄, and the solvent is removed invacuo.

The product is washed by stirring with hot toluene and filtered off withsuction.

Yield: 72 g (190 mmol), 92% of theory, purity according to ¹H-NMR about98%.

[2-(3-Bromocarbazol-9-yl)phenyl]diphenylmethanol

21.3 g (86.7 mmol) of Ce(III) chloride are initially introduced in 250ml of THF. 30 g (78.9 mmol) of methyl 2-(3-bromo-9H-carbazole)benzoate(dissolved in 600 ml of dried THF) are added dropwise to this solutionat room temperature, and the mixture is stirred for 2.5 hours. Themixture is cooled to 0° C., and 118.3 ml (236 mmol) of 2 Mphenylmagnesium bromide in THF are added, and the mixture is stirredovernight. When the reaction is complete, it is carefully quenched at−30° C. using MeOH. The reaction solution is evaporated to ⅓, 1 l ofCH₂Cl₂ is added, and the mixture is washed. The organic phase issubsequently dried over MgSO₄ and evaporated.

Yield: 38.7 g (76.7 mmol), 97% of theory, purity according to ¹H-NMRabout 94%.

Bromo-8,8-diphenyl-8H-indolo[3,2,1-de]acridine

38.7 g (76.7 mmol) of 2-[2-(3-bromocarbazol-9-yl)phenyl]propan-2-ol aredissolved in 750 ml of degassed dichloromethane, a suspension of 49.6 gof polyphosphoric acid and 33 ml of methanesulfonic acid is added, andthe mixture is heated at 60° C. for 1 h. The batch is cooled, and wateris added. A solid precipitates out and is dissolved in CH₂Cl₂/THF (1:1).The solution is carefully rendered alkaline using 20% NaOH, and thephases are separated and dried over MgSO₄. The solid obtained is washedby stirring with heptane. Yield: 22 g (45 mmol), 59% of theory, purityaccording to ¹H-NMR about 95%.

The following compounds are obtained analogously:

Starting Starting Ex. material 1 material 2 Product Yield 25a

63% 25b

74% 25c

59%

Example 26: 8,8-Diphenyl-8H-Indolo[3,2,1-de]acridine-6-boronic acid

125.9 g (259 mmol) of bromo-8,8-diphenyl-8H-indolo[3,2,1-de]acridine aredissolved in 1500 ml of dry THF. 135 ml (337 mmol) of a 2.5 M solutionof n-butyllithium in cyclohexane are added dropwise at −70° C., and,after 1 h, 37 ml of trimethyl borate (336 mmol) are added dropwise. Themixture is warmed to room temperature over the course of 1 h, thesolvent is removed, and the residue, which is uniform according to¹H-NMR, is employed in the subsequent reaction without furtherpurification.

Yield: 87.6 g (194 mmol), 75% of theory, purity according to ¹H-NMRabout 96%.

The following compounds are obtained analogously:

Ex. Starting material Product Yield 26a

61% 26b

55% 26c

56% 26d

51%

Example 27:Biphenyl-4-yl-(4-bromophenyl)-(9,9-dimethyl-9H-fluoren-2-yl)amine

A degassed solution of 24.6 g (87 mmol) of 1-bromo-4-iodobenzene and28.8 g (80 mmol) of biphenyl-4-yl-(9,9-dimethyl-9H-fluoren-2-yl)amine in1000 ml of dioxane is saturated with N₂ for 1 h. Then firstly 0.9 ml(4.3 mmol) of P(tBu)₃, then 0.48 g (2.1 mmol) of palladium(II) acetateare added to the solution. 12.6 g (131 mmol) of NaOtBu in the solidstate are subsequently added. The reaction mixture is heated underreflux for 18 h. After cooling to room temperature, 1000 ml of water arecarefully added. The organic phase is washed with 4×50 ml of water anddried over MgSO₄, and the solvent is removed in vacuo. The pure productis obtained by recrystallisation and final sublimation.

Yield: 31.5 g (61 mmol), 70% of theory, purity according to HPLC 98%.

Example 28:Biphenyl-4-yl-(9,9-dimethyl-9H-fluoren-2-yl)-[4-(8,8-diphenyl-8H-Indolo[3,2,1-de]acridin-3-yl)phenyl]amine(HTM14)

85 g (190 mmol) of 8,8-diphenyl-8H-indolo[3,2,1-de]acridine-3-boronicacid, 98 g (190 mmol) ofbiphenyl-4-yl-(4-bromophenyl)-(9,9-dimethyl-9H-fluoren-2-yl)amine and 13g (123 mmol) of sodium carbonate are suspended in 180 ml of toluene, 180ml of dioxane and 60 ml of water. 3.0 mg mmol) of Pd(PPh₃)₄ are added tothis suspension, and the reaction mixture is heated under reflux for 16h. After cooling, the organic phase is separated off, filtered throughsilica gel, washed three times with 200 ml of water and subsequentlyevaporated to dryness. The residue is recrystallised from toluene andfrom dichloromethane/isopropanol and finally sublimed in a high vacuum.The purity is 99.9%. The yield is 124 g (147 mmol), corresponding to 78%of theory.

The following compounds are obtained analogously:

Ex. Starting material Product Yield 28a

64% 28b

62% 28c

63% 28d

68% 28e

59% 28f

57% 28g

52% 28h

55% 28i

75% 28j

66% 28k

64%

Example 29: (8,8-Diphenyl-8H-indolo[3,2,1-de]acridin-3-yl)diphenylamine(HTM21)

A degassed solution of 42 g (86.6 mmol) of3-bromo-8,8-diphenyl-8H-indolo[3,2,1-de]acridine and 16 g (95.9 mmol) ofdiphenylamine in 1000 ml of dioxane is saturated with N₂ for 1 h. Thenfirstly 0.9 ml (4.3 mmol) of P(tBu)₃, then 0.48 g (2.1 mmol) ofpalladium(II) acetate are added, and 12.6 g (131 mmol) of NaOtBu in thesolid state are subsequently added to the solution. The reaction mixtureis heated under reflux for 18 h. After cooling to room temperature, 1000ml of water are carefully added. The organic phase is washed with 4×50ml of water and dried over MgSO₄, and the solvent is removed in vacuo.The pure product is obtained by recrystallisation and final sublimation.

Yield: 39 g (69 mmol), 80% of theory, purity according to HPLC 99.9%.

The following compounds are obtained analogously:

Starting Ex. material Product Yield 29a

64% 29b

72% 29c

61% 29d

66% 29e

72% 29f

67% 29g

58%

Example 30:3-(9,9-Dimethyl-10-phenyl-9,10-dihydroacridin-2-yl)-8,8-dimethyl-8H-indolo[3,2,1-de]acridine2-Chloro-9,9-dimethyl-9,10-dihydroacridine

30.3 g (116 mmol) of 2-[2-(4-chlorophenylamino)phenyl]propan-2-ol aredissolved in 700 ml of degassed toluene, a suspension of 93 g ofpolyphosphoric acid and 61.7 g of methanesulfonic acid is added, and themixture is stirred at room temperature for 1 h and heated at 50° C. for1 h. The batch is cooled and poured onto ice and extracted three timeswith ethyl acetate. The combined organic phases are washed withsaturated sodium chloride solution, dried over magnesium sulfate andevaporated. Filtration of the crude product through silica gel withheptane/ethyl acetate (20:1) gives 25.1 g (89%) of2-chloro-9,9-dimethyl-9,10-dihydroacridine as pale-yellow crystals.

2-Chloro-9,9-dimethyl-10-phenyl-9,10-dihydroacridine

A degassed solution of 16.6 ml (147 mmol) of 4-iodobenzene and 30 g (123mmol) of 2-chloro-9,9-dimethyl-9,10-dihydroacridine in 600 ml of tolueneis saturated with N₂ for 1 h. Then firstly 2.09 ml (8.6 mmol) of P(tBu)₃and then 1.38 g (6.1 mmol) of palladium(II) acetate are added to thesolution. 17.7 g (185 mmol) of NaOtBu as solid are subsequently added.The reaction mixture is heated under reflux for 1 h. After cooling toroom temperature, 500 ml of water are carefully added. The aqueous phaseis washed with 3×50 ml of toluene and dried over MgSO₄, and the solventis removed in vacuo. Filtration of the crude product through silica gelwith heptane/ethyl acetate (20:1) gives 32.2 g (81%) of2-chloro-9,9-dimethyl-10-phenyl-9,10-dihydroacridine as pale-yellowcrystals.

3-(9,9-Dimethyl-10-phenyl-9,10-dihydroacridin-2-yl)-8,8-dimethyl-8H-indolo[3,2,1-de]acridine

36 g (110 mmol) of 8,8-dimethyl-8H-indolo[3,2,1-de]acridine-3-boronicacid, 35.2 g (110 mmol) of2-chloro-9,9-dimethyl-10-phenyl-9,10-dihydroacridine and 9.7 g (92 mmol)of sodium carbonate are suspended in 350 ml of toluene, 350 ml ofdioxane and 500 ml of water. 913 mg (3.0 mmol) of tri-o-tolylphosphineand 112 mg (0.5 mmol) of palladium(II) acetate are added to thissuspension, and the reaction mixture is heated under reflux for 16 h.After cooling, the organic phase is separated off, filtered throughsilica gel, washed three times with 200 ml of water and subsequentlyevaporated to dryness. The residue is recrystallised from toluene andfrom CH₂Cl₂/isopropanol and finally sublimed in a high vacuum.

Yield: 52 g (100 mmol), 91% of theory, purity according to HPLC 99.9%.

B) Device Examples C1-I63: Production of OLEDs

OLEDs according to the invention and OLEDs in accordance with the priorart are produced by a general process in accordance with WO 04/058911,which is adapted to the circumstances described here (layer-thicknessvariation, materials used).

Data for various OLEDs are presented in the examples C1 to 163 below(see Tables 1-3). Glass plates coated with structured ITO (indium tinoxide) in a thickness of 150 nm are coated with 20 nm of PEDOT(poly(3,4-ethylenedioxy-2,5-thiophene, applied by spin coating fromwater; purchased from H. C. Starck, Goslar, Germany) for improvedprocessing. These coated glass plates form the substrates, to which theOLEDs are applied. The OLEDs have in principle the following layerstructure: substrate/optional hole-injection layer (HIL)/hole-transportlayer (HTL)/optional interlayer (IL)/electron-blocking layer(EBL)/emission layer (EML)/optional hole-blocking layer(HBL)/electron-transport layer (ETL) I/optional electron-injection layer(EIL) and finally a cathode. The cathode is formed by an aluminium layerwith a thickness of 100 nm. The precise structure of the OLEDs is shownin Table 1. The materials required for the production of the OLEDs areshown in Table 4.

All materials are applied by thermal vapour deposition in a vacuumchamber. The emission layer here always consists of at least one matrixmaterial (host material) and an emitting dopant (emitter), which isadmixed with the matrix material or materials in a certain proportion byvolume by coevaporation. An expression such as H3:CBP:TER1 (55%:35%:10%)here means that material H3 is present in the layer in a proportion byvolume of 55%, CBP is present in the layer in a proportion of 35% andTER1 is present in the layer in a proportion of 10%. Analogously, theelectron-transport layer may also consist of a mixture of two materials.

The OLEDs are characterised by standard methods. For this purpose, theelectroluminescence spectra, the current efficiency (measured in cd/A),the power efficiency (measured in Im/W) and the external quantumefficiency (EQE, measured in percent) as a function of the luminousdensity, calculated from current-voltage-luminance characteristic lines(IUL characteristic lines), and the lifetime are determined. Thelifetime is defined as the time after which the luminous density hasdropped to a certain proportion from a particular initial luminousdensity. The designation LD80 means that the said lifetime is the timeat which the luminous density has dropped to 80% of the initial luminousdensity, i.e. from, for example, 4000 cd/m² to 3200 cd/m². Analogously,LD50 denotes the time after which the initial luminance has dropped tohalf. The values for the lifetime can be converted to a figure for otherinitial luminous densities with the aid of conversion formulae known tothe person skilled in the art. The lifetime for an initial luminousdensity of 1000 cd/m² is a usual expression here.

OLEDs which comprise the blue-fluorescent emitter D1 are started at aninitial luminous density of 6000 cd/m² for determination of thelifetime. OLEDs which comprise the green-fluorescent emitter D2 arestarted at a luminous density of 25,000 cd/m². OLEDs comprising thephosphorescent emitters TER1 and TEG1 are started at 4000 cd/m².

The data for the various OLEDs are summarised in Tables 2 and 3.Examples C1-C22 are comparative examples in accordance with the priorart, Examples I1-I63 show data for OLEDs in which materials according tothe invention are employed.

Some of the examples are explained in greater detail below in order toillustrate the advantages of the compounds according to the invention.However, it should be pointed out that this only represents a selectionof the data shown in Tables 2 and 3. As can be seen from the table,significant improvements over the prior art are also achieved on use ofthe compounds according to the invention that are not described ingreater detail, in some cases in all parameters, but in some cases onlyan improvement in the efficiency or voltage or lifetime is observed.However, even the improvement in one of the said parameters represents asignificant advance.

Use of Compounds According to the Invention as Hole-Transport orElectron-Blocking Materials

The materials according to the invention can be employed in accordancewith the invention, inter alia, on the hole-transport side of OLEDs,more precisely as hole-transport or electron-blocking materials. This isshown with reference to Examples I1-I26, I40-I55, I57. ComparativeExamples C1-C9, C11, C12 and C19-C22 in accordance with the prior artcomprise materials HTM1 and HTM12 as hole-transport materials and NPB,EBM1, HTM11 and HTM12 as electron-blocking materials.

If Example I1 is compared with Example C3, it can be seen that theoperating voltage can be reduced by 0.2 V through the use of materialHTM8 according to the invention in the hole-transport layer, which, incombination with slightly improved quantum efficiency, results in animprovement in the power efficiency from 10.7 lm/W to 12.1 lm/W, i.e. byabout 15%. A similar improvement is also observed in the case of ahole-transport layer with a thickness of 200 nm (Examples C5 and I2).Furthermore, it is evident that the difference between the voltage for athick HTL (200 nm) and a thinner HTL (110 nm) reduces from 0.5 V(Examples C3 and C5) to 0.3 V (Examples I1 and I2). This is an importantaspect, since thicker hole-transport layers are often desirable foroptimisation of the optical coupling-out. It is desirable here for theoperating voltage to remain as low as possible. A further advantage ofmaterial HTM8 is the increase in the lifetime. In the case of a layerwith a thickness of 110 nm, although the improvement is 10%, materialHTM1 in accordance with the prior art exhibits a significant drop in thelifetime to 250,000 h in an OLED having an HTL with a thickness of 200nm compared with an OLED having an HTL with a thickness of 110 nm, whilean OLED comprising 200 nm of the material according to the inventioneven exhibits a slight improvement in the lifetime to 340,000 h(Examples C3, C5, I1 and I2). Compared with the triarylamine-substitutedcompound HTM12 in accordance with the prior art, material HTM8 exhibitsan even more significant improvement in the performance data (ExamplesC19, C20, I1 and I2).

If HTM3 is used as electron-blocking material together with fluorescentdopants D1 and D2, a significant improvement in the operating voltageand efficiency is obtained compared with NPB (Examples C1-3, C5, I3-I6).However, it is much more important that the lifetime can be increasedthrough the use of HTM3 in the case of blue emission (Examples Cl, C2,I3 and I4) to about 7700 h compared with 5200 h with NPB (with ETM1 aselectron-transport material). This corresponds to a significant increaseof 50%. In the case of green emission, the improvement in the lifetimeis somewhat less, with an increase of about 25% being obtained (ExamplesC3, C5, I5 and I6). Similar improvements can be achieved through the useof compound HTM2 according to the invention (Examples I7-I9). Inparticular, a combination of the novel materials HTM8 as hole-transportmaterial and HTM3 as electron-blocking material gives very goodperformance data: compared with the prior art, the lifetime is improvedby about 50% and the power efficiency by about 25% (Examples C2 andI12).

Furthermore, the compounds according to the invention can also beemployed as single layers, which represents a significant advantage overthe combination of HTM1 and NPB with respect to the processingcomplexity. This is demonstrated with reference to materials HTM2 andHTM3 in combination with the blue-fluorescent dopant D1. Although thetwo-layer structure HTM1/HTM2 (Ex. 18) or HTM1/HTM3 (Ex. 14) exhibits abetter voltage and efficiency than the single layer (Examples I10 andI11), the single layer is, however, still significantly superior to theprior art (Ex. C2) with respect to the lifetime. The voltage andefficiency are approximately the same.

In phosphorescent OLEDs, the compounds according to the inventionexhibit, in particular, a significant improvement in the lifetime and animprovement in the quantum or current efficiency on use aselectron-blocking layer (Examples C4, C6-C9, C1, C12 and I13-I26, I41,I43, I44, I46, I50-I53, I57). For example, if compound HTM3 according tothe invention is used in an OLED comprising the green-phosphorescentemitter TEG1, the lifetime is increased by up to more than 60% comparedwith material EBM1 in accordance with the prior art (Examples C12 andI17). The quantum efficiency is increased by about 10%, which, owing tothe virtually unchanged operating voltage, has the consequence that thepower efficiency is also increased by about 10%. The increase inefficiency can be explained by the greater triplet gap of the compoundsaccording to the invention. Compared with materials HTM11 and HTM12 inaccordance with the prior art, significant improvements likewise ariseon use of HTM3 as electron-blocking material (Examples C21, C22 andI15). The other materials according to the invention exhibit similarimprovements compared with the prior art. In the case of red emission,the compounds according to the invention exhibit, in particular, asignificant improvement in the lifetime compared with NPB in accordancewith the prior art (Examples C4, C6, 125 and I26).

Thus, the use of compounds according to the invention on thehole-transport side of OLEDs produces significant improvements, inparticular with respect to the lifetime and the operating voltage, powerefficiency, lifetime and processing complexity.

Use of Compounds According to the Invention as Component in Mixed-MatrixSystems

Mixed-matrix systems, i.e. OLEDs having an emission layer consisting ofthree or more components, in some cases exhibit significant advantagesover systems comprising single-matrix materials. The said systems aredescribed in detail, inter alia, in the application WO 10/108579. Thecompounds can also be employed in such systems in accordance with thepresent invention. Compared with mixed-matrix components in accordancewith the prior art, significant improvements arise with respect to theefficiency, voltage and lifetime. The compounds in accordance with theprior art used are the materials CBP, TCTA and FTPh (see Table 4). Thecorresponding OLEDs are denoted by C6, C10 and C14-C18. The materialsaccording to the invention employed are compounds H5-H17 in combinationwith matrix materials H3, Ket1 and DAP1. The corresponding OLEDs aredenoted by I27-I39, I56, I58-I63.

Firstly, mixed-matrix systems comprising the green-emitting dopant TEG1are compared. On replacement of CBP or TCTA with the compounds accordingto the invention, a significant improvement is observed in the operatingvoltage, power efficiency and especially also the lifetime. On use ofcompound H10 according to the invention in combination with H3, forexample, the power efficiency is increased by 60% compared with the useof CBP and by about 70% compared with TCTA (Examples C10, C18 and 127).The lifetime is increased by almost 60% compared with CBP, and virtuallya quadrupling of the lifetime is observed compared with TCTA. Similarimprovements are also obtained on combination of H10 with the ketonematrix Ket1 and diazaphosphole matrix DAP1 (Examples C14-C17, I28 andI29). Very good lifetimes can also be achieved with compounds H12 andH14, in which the bridge atoms are substituted by phenyl rings (ExamplesI58, I60). Other compounds according to the invention also exhibitsignificant improvements with respect to the voltage, power efficiencyand lifetime.

In red-emitting mixed-matrix systems, significant improvements arelikewise obtained on use of the compounds according to the invention(cf. Example C6 with I37-I39, I62, I63). On replacement of CBP with H10,for example, an improvement in the voltage of 1.1 V, an increase in thepower efficiency by about 50% and a virtually doubled lifetime areobtained (Examples C6 and I37). Similarly good performance data can beachieved with compounds H7 and H9 according to the invention.Furthermore, significant improvements compared with the prior art arealso obtained with compounds H16 and H17, which are substituted byphenyl rings on the bridge atoms (I62, I63).

The use of materials according to the invention in mixed-matrix systemsthus produces significant improvements with respect to the voltage,efficiency and especially also the lifetime of the OLEDs. Theseimprovements can be achieved in combination with very different classesof matrix materials (ketones: Ket1, spirotriazines: H3, diazaphospholes:DAP1). It can thus be assumed that similar improvements are alsoachievable through combination of the compounds according to theinvention with other classes of material.

TABLE 1 Structure of the OLEDs HIL HTL EML EIL Ex. Thickness ThicknessIL Thickness EBL Thickness Thickness HBL Thickness ETL ThicknessThickness C1 HIL1 5 nm HTM1 — NPB H1:D1 (95%:5%) — Alq₃ LiF 1 nm 140 nm20 nm 30 nm 20 nm C2 HIL1 5 nm HTM1 — NPB H1:D1 (95%:5%) — ETM1:LiQ —140 nm 20 nm 30 nm (50%:50%) 20 nm C3 HIL1 5 nm HTM1 — NPB H2:D2(90%:10%) — Alq₃ LiF 1 nm 110 nm 20 nm 30 nm 20 nm C4 — HTM1 — NPBH3:TER1 (85%:15%) — Alq₃ LiF 1 nm  20 nm 20 nm 30 nm 20 nm C5 HIL1 5 nmHTM1 — NPB H2:D2 (90%:10%) — Alq₃ LiF 1 nm 200 nm 20 nm 30 nm 20 nm C6 —HTM1 — NPB H3:CBP:TER1 H3 Alq₃ LiF 1 nm  20 nm 20 nm (45%:45%:10%) 30 nm10 nm 20 nm C7 — HTM1 — EBM1 H3:TEG1 (90%:10%) H3 ETM1:LiQ — 160 nm 20nm 30 nm 10 nm (50%:50%) 30 nm C8 — HTM1 — EBM1 H3:TEG1 (90%:10%) —ETM1:LiQ — 160 nm 20 nm 30 nm (50%:50%) 40 nm C9 — HTM1 HIL1 5 nm EBM1H4:TEG1 (85%:15%) — H3:LiQ (50%:50%) —  70 nm 90 nm 30 nm 40 nm C10 —HTM1 HIL1 5 nm EBM1 H3:CBP:TEG1 H3 10 nm H3:LiQ (50%:50%) —  70 nm 90 nm(30%:60%:10%) 30 nm 30 nm C11 — HTM1 HIL1 5 nm EBM1 H3:TEG1 (90%:10%) H3H3:LiQ (50%:50%) —  70 nm 90 nm 30 nm 10 nm 30 nm C12 — HTM1 HIL1 5 nmEBM1 H3:TEG1 (90%:10%) — H3:LiQ (50%:50%) —  70 nm 90 nm 30 nm 40 nm C14HIL1 — — EBM1 Ket1:FTPh:TEG1 Ket1 ETM2 LiF 20 nm 20 nm (60%:30%:10%) 30nm 10 nm 20 nm 1 nm C15 HIL1 — — EBM1 Ket1:TCTA:TEG1 Ket1 ETM2 LiF 20 nm20 nm (60%:30%:10%) 30 nm 10 nm 20 nm 1 nm C16 HIL1 — — EBM1Ket1:CBP:TEG1 Ket1 ETM2 LiF 20 nm 20 nm (60%:30%:10%) 30 nm 10 nm 20 nm1 nm C17 — HTM1 HIL1 5 nm EBM1 DAP1:CBP:TEG1 — H3:LiQ (50%:50%) —  70 nm90 nm (30%:60%:10%) 30 nm 30 nm C18 — HTM1 HIL1 5 nm EBM1 H3:TCTA:TEG1 —H3:LiQ (50%:50%) —  70 nm 90 nm (30%:60%:10%) 30 nm 30 nm C19 HIL1 5 nmHTM12 — NPB H2:D2 (90%:10%) — Alq₃ LiF 1 nm 110 nm 20 nm 30 nm 20 nm C20HIL1 5 nm HTM12 — NBP H2:D2 (90%:10%) — Alq₃ LiF 1 nm 200 nm 20 nm 30 nm20 nm C21 — HTM1 HIL1 5 nm HTM11 H4:TEG1 (85%:15%) — H3:LiQ (50%:50%) — 70 nm 90 nm 30 nm 40 nm C22 — HTM1 HIL1 5 nm HTM12 H4:TEG1 (85%:15%) —H3:LiQ (50%:50%) —  70 nm 90 nm 30 nm 40 nm I1 HIL1 5 nm HTM8 — NPBH2:D2 (90%:10%) — Alq₃ LiF 1 nm 110 nm 20 nm 30 nm 20 nm I2 HIL1 5 nmHTM8 — NPB H2:D2 (90%:10%) — Alq₃ LiF 1 nm 200 nm 20 nm 30 nm 20 nm I3HIL1 5 nm HTM1 — HTM3 H1:D1 (95%:5%) — Alq₃ LiF 1 nm 140 nm 20 nm 30 nm20 nm I4 HIL1 5 nm HTM1 — HTM3 H1:D1 (95%:5%) — ETM1:LiQ — 140 nm 20 nm30 nm (50%:50%) 20 nm I5 HIL1 5 nm HTM1 — HTM3 H2:D2 (90%:10%) — Alq₃LiF 1 nm 110 nm 20 nm 30 nm 20 nm I6 HIL1 5 nm HTM1 — HTM3 H2:D2(90%:10%) — Alq₃ LiF 1 nm 200 nm 20 nm 30 nm 20 nm I7 HIL1 5 nm HTM1 —HTM2 H1:D1 (95%:5%) — Alq₃ LiF 1 nm 140 nm 20 nm 30 nm 20 nm I8 HIL1 5nm HTM1 — HTM2 H1:D1 (95%:5%) — ETM1:LiQ — 140 nm 20 nm 30 nm (50%:50%)20 nm I9 HIL1 5 nm HTM1 — HTM2 H2:D2 (90%:10%) — Alq₃ LiF 1 nm 110 nm 20nm 30 nm 20 nm I10 HIL1 5 nm — — HTM2 H1:D1 (95%:5%) — ETM1:LiQ — 160nm  30 nm (50%:50%) 20 nm I11 HIL1 5 nm — — HTM3 H1:D1 (95%:5%) —ETM1:LiQ — 160 nm  30 nm (50%:50%) 20 nm I12 HIL1 5 nm HTM8 — HTM3 H1:D1(95%:5%) — ETM1:LiQ — 140 nm 20 nm 30 nm (50%:50%) 20 nm I13 — HTM1 —HTM3 H3:TEG1 (90%:10%) H3 ETM1:LiQ — 160 nm 20 nm 30 nm 10 nm (50%:50%)30 nm I14 — HTM1 — HTM3 H3:TEG1 (90%:10%) — ETM1:LiQ — 160 nm 20 nm 30nm (50%:50%) 40 nm I15 — HTM1 HIL1 5 nm HTM3 H4:TEG1 (85%:15%) — H3:LiQ(50%:50%) —  70 nm 90 nm 30 nm 40 nm I16 — HTM1 HIL1 5 nm HTM3 H3:TEG1(90%:10%) H3 H3:LiQ (50%:50%) —  70 nm 90 nm 30 nm 10 nm 30 nm I17 —HTM1 HIL1 5 nm HTM3 H3:TEG1 (90%:10%) — H3:LiQ (50%:50%) —  70 nm 90 nm30 nm 40 nm I18 — HTM1 HIL1 5 nm HTM2 H4:TEG1 (85%:15%) — H3:LiQ(50%:50%) —  70 nm 90 nm 30 nm 40 nm I19 — HTM1 HIL1 5 nm HTM4 H4:TEG1(85%:15%) — H3:LiQ (50%:50%) —  70 nm 90 nm 30 nm 40 nm I20 — HTM1 HIL15 nm HTM5 H4:TEG1 (85%:15%) — H3:LiQ (50%:50%) —  70 nm 90 nm 30 nm 40nm I21 — HTM1 HIL1 5 nm HTM6 H4:TEG1 (85%:15%) — H3:LiQ (50%:50%) —  70nm 90 nm 30 nm 40 nm I22 — HTM1 HIL1 5 nm HTM7 H4:TEG1 (85%:15%) —H3:LiQ (50%:50%) —  70 nm 90 nm 30 nm 40 nm I23 — HTM1 HIL1 5 nm HTM9H4:TEG1 (85%:15%) — H3:LiQ (50%:50%) —  70 nm 90 nm 30 nm 40 nm I24 —HTM1 HIL1 5 nm HTM10 H4:TEG1 (85%:15%) — H3:LiQ (50%:50%) —  70 nm 90 nm30 nm 40 nm I25 — HTM1 — HTM3 H3:TER1 (85%:15%) — Alq₃ LiF 1 nm  20 nm20 nm 30 nm 20 nm I26 — HTM1 — HTM3 H3:CBP:TER1 H3 Alq₃ LiF 1 nm  20 nm20 nm (45%:45%:10%) 30 nm 10 nm 20 nm I27 — HTM1 HIL1 5 nm EBM1H3:H10:TEG1 H3 10 nm H3:LiQ (50%:50%) —  70 nm 90 nm (30%:60%:10%) 30 nm30 nm I28 HIL1 — — EBM1 Ket1:H10:TEG1 Ket1 ETM2 LiF 20 nm 20 nm(60%:30%:10%) 30 nm 10 nm 20 nm 1 nm I29 — HTM1 HIL1 5 nm EBM1DAP1:H10:TEG1 — H3:LiQ (50%:50%) —  70 nm 90 nm (30%:60%:10%) 30 nm 30nm I30 — HTM1 HIL1 5 nm EBM1 H3:H7:TEG1 H3 10 nm H3:LiQ (50%:50%) —  70nm 90 nm (30%:60%:10%) 30 nm 30 nm I31 HIL1 — — EBM1 Ket1:H7:TEG1 Ket1ETM2 LiF 20 nm 20 nm (60%:30%:10%) 30 nm 10 nm 20 nm 1 nm I32 — HTM1HIL1 5 nm EBM1 DAP1:H7:TEG1 — H3:LiQ (50%:50%) —  70 nm 90 nm(30%:60%:10%) 30 nm 30 nm I33 — HTM1 HIL1 5 nm EBM1 H3:H5:TEG1 H3 10 nmH3:LiQ (50%:50%) —  70 nm 90 nm (30%:60%:10%) 30 nm 30 nm I35 — HTM1HIL1 5 nm EBM1 H3:H8:TEG1 H3 10 nm H3:LiQ (50%:50%) —  70 nm 90 nm(30%:60%:10%) 30 nm 30 nm I36 — HTM1 HIL1 6 nm EBM1 H3:H9:TEG1 H3 10 nmH3:LiQ (50%:50%) —  70 nm 90 nm (30%:60%:10%) 30 nm 30 nm I37 — HTM1 —NPB H3:H10:TER1 H3 Alq₃ LiF 1 nm  20 nm 20 nm (45%:45%:10%) 30 nm 10 nm20 nm I38 — HTM1 — NPB H3:H7:TER1 H3 Alq₃ LiF 1 nm  20 nm 20 nm(45%:45%:10%) 30 nm 10 nm 20 nm I39 — HTM1 — NPB H3:H9:TER1 H3 Alq₃ LiF1 nm  20 nm 20 nm (45%:45%:10%) 30 nm 10 nm 20 nm I40 HIL1 5 nm HTM1 —HTM13 H1:D1 (95%:5%) — ETM1:LiQ — 140 nm 20 nm 30 nm (50%:50%) 20 nm I41— HTM1 HIL1 5 nm HTM13 H4:TEG1 (85%:15%) — H3:LiQ (50%:50%) —  70 nm 90nm 30 nm 40 nm I42 HIL1 5 nm HTM1 — HTM14 H1:D1 (95%:5%) — ETM1:LiQ —140 nm 20 nm 30 nm (50%:50%) 20 nm I43 — HTM1 HIL1 5 nm HTM14 H4:TEG1(85%:15%) — H3:LiQ (50%:50%) —  70 nm 90 nm 30 nm 40 nm I44 — HTM1 HIL15 nm HTM15 H4:TEG1 (85%:15%) — H3:LiQ (50%:50%) —  70 nm 90 nm 30 nm 40nm I45 HIL1 5 nm HTM17 — NPB H2:D2 (90%:10%) — Alq₃ LiF 1 nm 110 nm 20nm 30 nm 20 nm I46 — HTM1 HIL1 5 nm HTM18 H4:TEG1 (85%:15%) — H3:LiQ(50%:50%) —  70 nm 90 nm 30 nm 40 nm I47 HIL1 5 nm HTM19 — NPB H2:D2(90%:10%) — Alq₃ LiF 1 nm 110 nm 20 nm 30 nm 20 nm I48 HIL1 5 nm HTM1 —HTM20 H1:D1 (95%:5%) — ETM1:LiQ — 140 nm 20 nm 30 nm (50%:50%) 20 nm I49HIL1 5 nm HTM1 — HTM20 H2:D2 (90%:10%) — Alq₃ LiF 1 nm 110 nm 20 nm 30nm 20 nm I50 — HTM1 HIL1 6 nm HTM21 H4:TEG1 (85%:15%) — H3:LiQ (50%:50%)—  70 nm 90 nm 30 nm 40 nm I51 — HTM1 HIL1 5 nm HTM22 H4:TEG1 (85%:15%)— H3:LiQ (50%:50%) —  70 nm 90 nm 30 nm 40 nm I52 — HTM1 HIL1 5 nm HTM23H4:TEG1 (85%:15%) — H3:LiQ (50%:50%) —  70 nm 90 nm 30 nm 40 nm I53 —HTM1 HIL1 5 nm HTM24 H4:TEG1 (85%:15%) — H3:LiQ (50%:50%) —  70 nm 90 nm30 nm 40 nm I54 HIL1 5 nm HTM25 — NPB H2:D2 (90%:10%) — Alq₃ LiF 1 nm110 nm 20 nm 30 nm 20 nm I55 HIL1 5 nm HTM1 — HTM26 H2:D2 (90%:10%) —Alq₃ LiF 1 nm 110 nm 20 nm 30 nm 20 nm I56 — HTM1 HIL1 5 nm EBM1H3:H11:TEG1 H3 10 nm H3:LiQ (50%:50%) —  70 nm 90 nm (30%:60%:10%) 30 nm30 nm I57 — HTM1 HIL1 5 nm HTM16 H4:TEG1 (85%:15%) — H3:LiQ (50%:50%) — 70 nm 90 nm 30 nm 40 nm I58 — HTM1 HIL1 5 nm EBM1 H3:H12:TEG1 H3 10 nmH3:LiQ (50%:50%) —  70 nm 90 nm (30%:60%:10%) 30 nm 30 nm I60 — HTM1HIL1 5 nm EBM1 H3:H14:TEG1 H3 10 nm H3:LiQ (50%:50%) —  70 nm 90 nm(30%:60%:10%) 30 nm 30 nm I62 — HTM1 — NPB H3:H16:TER1 H3 Alq₃ LiF 1 nm 20 nm 20 nm (45%:45%:10%) 30 nm 10 nm 20 nm I63 — HTM1 — NPBH3:H17:TER1 H3 Alq₃ LiF 1 nm  20 nm 20 nm (45%:45%:10%) 30 nm 10 nm 20nm

TABLE 2 Data of the OLEDs Voltage for Efficiency at Efficiency at EQE atCIE x/y at LD80 from Ex. 1000 cd/m² 1000 cd/m² 1000 cd/m² 1000 cd/m²1000 cd/m² 4000 cd/m² C1 6.4 V 5.1 cd/A 2.5 lm/W 4.2% 0.14/0.15 5500 hC2 4.7 V 8.1 cd/A 5.4 lm/W 6.3% 0.14/0.16 5200 h C3 5.0 V 17.1 cd/A 10.7lm/W 5.0% 0.28/0.61 300000 h C4 5.0 V 7.2 cd/A 4.5 lm/W 12.0% 0.69/0.3114000 h C5 5.5 V 15.9 cd/A 9.1 lm/W 4.8% 0.31/0.58 250000 h C6 5.2 V 8.1cd/A 4.9 lm/W 11.4% 0.68/0.32 15000 h C19 5.2 V 16.8 cd/A 10.1 lm/W 4.9%0.28/0.61 280000 h C20 5.7 V 15.5 cd/A 8.6 lm/W 4.7% 0.31/0.58 220000 hI1 4.8 V 18.6 cd/A 12.1 lm/W 5.4% 0.28/0.61 330000 h I2 5.1 V 17.2 cd/A10.6 lm/W 5.2% 0.30/0.59 340000 h I3 5.8 V 5.8 cd/A 3.2 lm/W 4.8%0.14/0.15 7800 h I4 4.4 V 8.8 cd/A 6.3 lm/W 6.8% 0.14/0.15 7700 h I5 4.7V 19.5 cd/A 13.0 lm/W 5.7% 0.28/0.61 380000 h I6 5.2 V 18.2 cd/A 11.0lm/W 5.5% 0.31/0.58 350000 h I7 6.0 V 5.7 cd/A 3.0 lm/W 4.7% 0.14/0.157100 h I8 4.7 V 8.5 cd/A 5.7 lm/W 6.6% 0.14/0.15 6700 h I9 4.8 V 19.1cd/A 12.5 lm/W 5.6% 0.28/0.61 340000 h I10 4.7 V 8.0 cd/A 5.3 lm/W 6.2%0.14/0.16 6700 h I11 4.6 V 8.3 cd/A 5.7 lm/W 6.5% 0.14/0.16 6300 h I124.2 V 9.1 cd/A 6.8 lm/W 7.0% 0.14/0.15 7900 h I25 4.9 V 7.5 cd/A 4.8lm/W 12.5% 0.69/0.31 21000 h I26 5.1 V 8.3 cd/A 5.1 lm/W 11.6% 0.68/0.3221000 h I37 4.1 V 9.6 cd/A 7.4 lm/W 13.3% 0.68/0.32 29000 h I38 4.0 V9.2 cd/A 7.2 lm/W 12.8% 0.68/0.32 27000 h I39 4.0 V 9.3 cd/A 7.3 lm/W13.0% 0.68/0.32 24000 h I40 4.6 V 9.0 cd/A 6.1 lm/W 7.0% 0.14/0.15 6500h I42 4.6 V 8.7 cd/A 6.0 lm/W 6.7% 0.14/0.16 7200 h I45 5.1 V 18.5 cd/A11.3 lm/W 5.4% 0.28/0.61 280000 h I47 4.9 V 17.5 cd/A 11.1 lm/W 5.1%0.28/0.61 310000 h I48 4.8 V 8.5 cd/A 5.6 lm/W 6.6% 0.14/0.16 6700 h I495.0 V 17.8 cd/A 11.2 lm/W 5.2% 0.28/0.61 340000 h I54 5.0 V 18.0 cd/A11.3 lm/W 5.3% 0.28/0.61 320000 h I55 4.9 V 18.8 cd/A 11.9 lm/W 5.5%0.28/0.81 340000 h I62 4.2 V 8.7 cd/A 6.5 lm/W 12.2% 0.68/0.32 19000 hI63 4.4 V 77.7 cd/A 5.5 lm/W 10.8% 0.68/0.32 16000 h

TABLE 3 Data of the OLEDs Voltage for Efficiency at Efficiency at EQE atCIE x/y at LD50 from Ex. 1000 cd/m² 1000 cd/m² 1000 cd/m² 1000 cd/m²1000 cd/m² 1000 cd/m² C7 4.7 V 55 cd/A 37 lm/W 16.4% 0.36/0.61 350 h C84.6 V 54 cd/A 37 lm/W 15.0% 0.37/0.60 320 h C9 3.6 V 52 cd/A 45 lm/W14.6% 0.37/0.60 430 h C10 4.4 V 48 cd/A 34 lm/W 13.3% 0.37/0.60 450 hC11 4.4 V 54 cd/A 39 lm/W 15.0% 0.36/0.60 320 h C12 4.3 V 55 cd/A 40 m/W15.3% 0.37/0.61 300 h C14 4.0 V 46 cd/A 36 lm/W 12.8% 0.36/0.61 430 hC15 3.9 V 42 cd/A 34 lm/W 11.6% 0.35/0.60 160 h C16 4.1 V 44 cd/A 34lm/W 12.3% 0.36/0.61 320 h C17 4.6 V 47 cd/A 32 lm/W 13.2% 0.36/0.60 480h C18 4.2 V 43 cd/A 32 lm/W 12.0% 0.35/0.60 190 h C21 3.6 V 55 cd/A 48lm/W 15.5% 0.37/0.60 450 h C22 3.9 V 46 cd/A 38 lm/W 12.9% 0.36/0.60 360h I13 4.7 V 61 cd/A 41 lm/W 17.0% 0.36/0.61 460 h I14 4.5 V 59 cd/A 41lm/W 16.4% 0.37/0.60 440 h I15 3.7 V 56 cd/A 48 lm/W 15.7% 0.37/0.60 670h I16 4.4 V 63 cd/A 45 lm/W 17.5% 0.36/0.61 510 h I17 4.6 V 61 cd/A 43lm/W 16.9% 0.37/0.61 500 h I18 3.9 V 62 cd/A 50 lm/W 17.4% 0.37/0.60 570h I19 3.7 V 64 cd/A 54 lm/W 17.9% 0.36/0.60 520 h I20 4.0 V 60 cd/A 47lm/W 16.7% 0.37/0.60 540 h I21 3.7 V 65 cd/A 52 lm/W 18.2% 0.37/0.60 550h I22 3.7 V 58 cd/A 49 lm/W 16.3% 0.36/0.60 490 h I23 3.8 V 56 cd/A 46lm/W 15.7% 0.36/0.61 470 h I24 3.5 V 57 cd/A 51 lm/W 16.0% 0.36/0.60 510h I27 3.2 V 56 cd/A 55 lm/W 15.8% 0.36/0.61 710 h I28 3.1 V 49 cd/A 50lm/W 13.8% 0.36/0.61 630 h I29 4.0 V 46 cd/A 36 lm/W 12.9% 0.36/0.60 640h I30 3.3 V 54 cd/A 52 lm/W 15.2% 0.36/0.61 680 h I31 3.1 V 50 cd/A 51lm/W 13.9% 0.36/0.61 590 h I32 4.1 V 48 cd/A 37 lm/W 13.5% 0.36/0.60 620h I33 3.3 V 56 cd/A 53 lm/W 15.7% 0.38/0.61 640 h I35 3.3 V 54 cd/A 52lm/W 15.3% 0.36/0.61 660 h I36 3.5 V 50 cd/A 45 lm/W 14.0% 0.36/0.61 620h I41 3.9 V 60 cd/A 49 lm/W 16.7% 0.36/0.60 640 h I43 3.8 V 56 cd/A 46lm/W 15.5% 0.36/0.60 610 h I44 3.6 V 61 cd/A 53 lm/W 16.8% 0.36/0.60 520h I46 3.8 V 60 cd/A 49 lm/W 16.5% 0.36/0.60 650 h I50 3.8 V 62 cd/A 51lm/W 17.2% 0.36/0.60 500 h I51 3.8 V 63 cd/A 52 lm/W 17.4% 0.36/0.60 560h I52 3.7 V 60 cd/A 50 lm/W 16.6% 0.36/0.60 510 h I53 3.9 V 55 cd/A 45lm/W 15.3% 0.36/0.60 450 h I56 3.7 V 49 cd/A 42 lm/W 13.7% 0.37/0.61 540h I57 4.0 V 57 cd/A 45 lm/W 15.8% 0.37/0.60 420 h I58 3.4 V 54 cd/A 49lm/W 14.8% 0.36/0.61 710 h I60 3.8 V 51 cd/A 42 lm/W 14.0% 0.37/0.61 660h

TABLE 4 Structural formulae of the materials used

HIL1

HTM1 (prior art)

NPB (prior art)

EBM1 (prior art)

HTM11 (prior art)

HTM12 (prior art)

Alq₃

H1

H2

D1

D2

ETM1

ETM2

CBP (prior art)

Ket1

TCTA (prior art)

DAP1

FTPh (prior art)

H3

H4

LIQ

TEG1

TER1

HTM2

H5

H7

HTM3

H8

HTM4

HTM5

HTM6

HTM7

HTM8

H9

HTM9

HTM10

H10

HTM13

HTM14

HTM15

HTM16

HTM17

HTM18

HTM19

HTM20

HTM21

HTM22

HTM23

HTM24

HTM25

HTM26

H11

H12

H14

H16

H17

The invention claimed is:
 1. A compound of the formula (I)

where the following applies to the symbols and indices occurring: Y ison each occurrence, identically or differently, a single bond or C(R²)₂,where at least one group Y which represents a single bond is present; Phis a phenyl group, which may be substituted by one or more radicals R¹;Ar¹ is an aromatic ring system having 6 to 30 aromatic ring atoms, whichmay be substituted by one or more radicals R¹; R¹, R² are on eachoccurrence, identically or differently, H, D, F, Cl, Br, I, CHO, N(R³)₂,C(═O)R³, P(═O)(R³)₂, S(═O)R³, S(═O)₂R³, CR³═C(R³)₂, CN, NO₂, Si(R³)₃,B(OR³)₂, OSO₂R³, OH, a straight-chain alkyl, alkoxy or thioalkyl grouphaving 1 to 40 C atoms or a branched or cyclic alkyl, alkoxy orthioalkyl group having 3 to 40 C atoms or an alkenyl or alkynyl grouphaving 2 to 40 C atoms, each of which may be substituted by one or moreradicals R₃, where one or more non-adjacent CH₂ groups may be replacedby R³C═CR³, C≡C, Si(R³)₂, Ge(R³)₂, Sn(R³)₂, C═O, C═S, C═Se, C═NR³,P(═O)(R³), SO, SO₂, NR³, O, S or CONR³ and where one or more H atoms maybe replaced by D, F, Cl, Br, I, CN or NO₂, or a mono- or polycyclicaromatic or heteroaromatic ring system having 5 to 60 aromatic ringatoms, which may in each case be substituted by one or more non-aromaticradicals R³, or an aryloxy or heteroaryloxy group having 5 to 60aromatic ring atoms, which may be substituted by one or morenon-aromatic radicals R³, or a combination of these systems, where twoor more radicals R¹ and/or R² may be linked to one another and may forma mono- or polycyclic, aliphatic or aromatic ring system; R³ is on eachoccurrence, identically or differently, H, D, F, Cl, Br, I, CHO, N(R⁴)₂,C(═O)R⁴, P(═O)(R⁴)₂, S(═O)R⁴, S(═O)₂R⁴, CR⁴═C(R⁴)₂, CN, NO₂, Si(R⁴)₃,B(OR⁴)₂, OSO₂R⁴, OH, a straight-chain alkyl, alkoxy or thioalkyl grouphaving 1 to 40 C atoms or a branched or cyclic alkyl, alkoxy orthioalkyl group having 3 to 40 C atoms or an alkenyl or alkynyl, grouphaving 2 to 40 C atoms, each of which may be substituted by one or moreradicals R⁴, where one or more non-adjacent CH₂ groups may be replacedby R⁴C═CR⁴, C≡C, Si(R⁴)₂, Ge(R⁴)₂, Sn(R⁴)₂, C═O, C═S, C═Se, C═NR⁴,P(═O)(R⁴), SO, SO₂, NR⁴, O, S or CONR⁴ and where one or more H atoms maybe replaced by D, F, Cl, Br, I, CN or NO₂, or a mono- or polycyclicaromatic or heteroaromatic ring system having 5 to 60 aromatic ringatoms, which may in each case be substituted by one or more non-aromaticradicals R⁴, or an aryloxy or heteroaryloxy group having 5 to 60aromatic ring atoms, which may be substituted by one or morenon-aromatic radicals R⁴, or a combination of these systems, where twoor more radicals R³ may be linked to one another and may form a mono- orpolycyclic, aliphatic or aromatic ring system; R⁴ is on each occurrence,identically or differently, H, D, F or an aliphatic, aromatic and/orheteroaromatic organic radical having 1 to 20 C atoms, in which, inaddition, one or more H atoms may be replaced by D or F; two or moreidentical or different substituents R⁴ here may also be linked to oneanother and may form a mono- or polycyclic, aliphatic or aromatic ringsystem; n is on each occurrence, identically or differently, 0 or 1,where the sum of the values of n is equal to 1 or 2 and where, for n=0,a group R¹ is bonded instead of a group Y; and where not more than onegroup R¹ which represents a group of the formula N(R³)₂, where R³ is anaryl group, may be bonded to a single triarylamine group in formula (I).2. The compound according to claim 1, wherein the sum of the values of nis equal to
 1. 3. The compound according to claim 1, wherein preciselyone group Y is a single bond and precisely one further group Y isC(R²)₂.
 4. The compound according to claim 1, wherein R¹ is selected oneach occurrence, identically or differently, from H, D, F, CN, Si(R³)₃or a straight-chain alkyl or alkoxy group having 1 to 20 C atoms or abranched or cyclic alkyl or alkoxy group having 3 to 20 C atoms, each ofwhich may be substituted by one or more radicals R³, where one or moreadjacent or non-adjacent CH₂ groups may be replaced by —C≡C—, R³C═CR³,Si(R³)₂, C═O, C═NR³, NR³, O, S, COO or CONR³, or an aryl or heteroarylgroup having 5 to 30 aromatic ring atoms, which may in each case besubstituted by one or more radicals R³.
 5. The compound according toclaim 1, wherein R² is selected on each occurrence, identically ordifferently, from H, D, a straight-chain alkyl group having 1 to 8carbon atoms, a branched alkyl group having 3 to 8 carbon atoms or anaryl group having 6 to 18 carbon atoms, where the said groups may eachbe substituted by one or more groups R³.
 6. The compound according toclaim 1, wherein at least one group R² which represents an aryl grouphaving 6 to 10 carbon atoms which is substituted by one or more radicalsR³ must be present.
 7. The compound according to claim 1, wherein R³ isselected on each occurrence, identically or differently, from H, D, F,CN, Si(R⁴)₃, N(R⁴)₂ or a straight-chain alkyl or alkoxy group having 1to 20 C atoms or a branched or cyclic alkyl or alkoxy group having 3 to20 C atoms, each of which may be substituted by one or more radicals R⁴,where one or more adjacent or non-adjacent CH₂ groups may be replaced by—C≡C—, R⁴C═CR⁴, Si(R⁴)₂, C═O, C═NR⁴, NR⁴, O, S, COO or CONR⁴, or an arylor heteroaryl group having 5 to 30 aromatic ring atoms, which may ineach case be substituted by one or more radicals R⁴.
 8. The compoundaccording to claim 1, wherein R⁴ is on each occurrence, identically ordifferently, H, D, F or an aliphatic, aromatic and/or heteroaromaticorganic radical having 1 to 20 C atoms, in which, in addition, one ormore H atoms may be replaced by D or F.
 9. The compound according toclaim 1, wherein Ar¹ conforms to a formula (Ar¹-1)

where the bonds to the group Ph and to the nitrogen atom are representedby the dashed lines, and where the group may be substituted in all freepositions by radicals R¹ as defined in claim
 1. 10. The compoundaccording to claim 1, wherein the group Ph conforms to one of theformulae (Ph-1) and (Ph-2):

where the bonds to the nitrogen atom and to the group Ar¹ arerepresented by the dashed lines, and the symbols # mark the position ofthe bond to a group Y, if present, and where the structures may besubstituted in all free positions by radicals R¹ as defined in claim 1.11. The compound according to claim 1, wherein the compound conforms toone of the following formulae (I-16) to (I-20):

where L is C(R²)₂; and R¹ is as defined in claim
 1. 12. An oligomer,polymer or dendrimer comprising one or more compounds according to claim1, where the bond(s) to the polymer, oligomer or dendrimer may belocalised at any desired positions substituted by R¹ or R² in formula(I).
 13. A formulation comprising at least one compound according toclaim 1 and at least one solvent.
 14. A formulation comprising at leastone polymer, oligomer or dendrimer according to claim 12 and at leastone solvent.
 15. A Process for the preparation of the compound accordingto claim 1, which comprises at least one ring-closure reaction iscarried out for the introduction of a bridging group Y or L.
 16. Anelectronic device comprising at least one compound according to claim 1.17. An electronic device comprising at least one polymer, oligomer ordendrimer according to claim
 12. 18. The electronic device according toclaim 16 wherein the device is selected from the group consisting oforganic integrated circuits (O-ICs), organic field-effect transistors(O-FETs), organic thin-film transistors (O-TFTs), organic light-emittingtransistors (O-LETs), organic solar cells (O-SCs), organic opticaldetectors, organic photoreceptors, organic field-quench devices(O-FQDs), light-emitting electrochemical cells (LECs), organic laserdiodes (O-lasers) and organic electroluminescent devices (OLEDs).
 19. Anorganic electroluminescent device comprising the compound according toclaim 1 is employed as hole-transport material in a hole-transport layeror hole-injection layer and/or as matrix material.
 20. An organicelectroluminescent device comprising the compound according to claim 1is employed as hole-transport material in a hole-transport layer orhole-injection layer and/or as matrix material, in combination with oneor more further matrix materials, in an emitting layer.